310
[1]
N. Yan, X. Chen, Don’t waste seafood waste. Turning cast-off shells into nitrogen-rich
311
chemicals would benefit economies and the environment, Nature. 524 (2015) 155–157.
312
https://doi.org/10.1038/524155a.
313
[2]
D. Raabe, C. Sachs, P. Romano, The crustacean exoskeleton as an example of a
314
structurally and mechanically graded biological nanocomposite material, Acta Mater.
315
53 (2005) 4281–4292. https://doi.org/10.1016/j.actamat.2005.05.027.
316
[3]
317
318
S. Ifuku, H. Saimoto, Chitin nanofibers: Preparations, modifications, and applications,
Nanoscale. 4 (2012) 3308–3318. https://doi.org/10.1039/c2nr30383c.
[4]
I.F. Nata, S.S.S. Wang, T.M. Wu, C.K. Lee, β-Chitin nanofibrils for self-sustaining
319
hydrogels preparation via hydrothermal treatment, Carbohydr. Polym. 90 (2012) 1509–
320
1514. https://doi.org/10.1016/j.carbpol.2012.07.022.
321
[5]
C. Chen, D. Li, Q. Hu, R. Wang, Properties of polymethyl methacrylate-based
322
nanocomposites: Reinforced with ultra-long chitin nanofiber extracted from crab
323
shells, Mater. Des. 56 (2014) 1049–1056.
324
https://doi.org/10.1016/j.matdes.2013.11.057.
325
[6]
S. Suenaga, M. Osada, Parameters of hydrothermal gelation of chitin nanofibers
326
determined using a severity factor, Cellulose. 25 (2018) 6873–6885.
327
https://doi.org/10.1007/s10570-018-2053-3.
328
[7]
S. Suenaga, M. Osada, Preparation of β-chitin nanofiber aerogels by lyophilization,
329
Int. J. Biol. Macromol. 126 (2019) 1145–1149.
330
https://doi.org/10.1016/j.ijbiomac.2019.01.006.
331
[8]
P. Sikorski, R. Hori, M. Wada, Revisit of α-chitin crystal structure using high
332
resolution X-ray diffraction data, Biomacromolecules. 10 (2009) 1100–1105.
333
https://doi.org/10.1021/bm801251e.
14
334
[9]
F.C. Yang, R.D. Peters, H. Dies, M.C. Rheinstädter, Hierarchical, self-similar structure
335
in native squid pen, Soft Matter. 10 (2014) 5541–5549.
336
https://doi.org/10.1039/c4sm00301b.
337
[10]
338
339
Y. Nishiyama, Y. Noishiki, M. Wada, X-ray structure of anhydrous β-chitin at 1 Å
resolution, Macromolecules. 44 (2011) 950–957. https://doi.org/10.1021/ma102240r.
[11]
D. Sawada, Y. Nishiyama, P. Langan, V.T. Forsyth, S. Kimura, M. Wada, Direct
340
determination of the hydrogen bonding arrangement in anhydrous β-chitin by neutron
341
fiber diffraction, Biomacromolecules. 13 (2012) 288–291.
342
https://doi.org/10.1021/bm201512t.
343
[12]
D. Sawada, Y. Nishiyama, P. Langan, V.T. Forsyth, S. Kimura, M. Wada, Water in
344
crystalline fibers of dihydrate β-chitin results in unexpected absence of intramolecular
345
hydrogen bonding, PLoS One. 7 (2012) 4–11.
346
https://doi.org/10.1371/journal.pone.0039376.
347
[13]
Y. Fan, T. Saito, A. Isogai, Preparation of chitin nanofibers from squid Pen β-chitin by
348
simple mechanical treatment under acid conditions, Biomacromolecules. 9 (2008)
349
1919–1923. https://doi.org/10.1021/bm800178b.
350
[14]
S. Suenaga, N. Nikaido, K. Totani, K. Kawasaki, Y. Ito, K. Yamashita, M. Osada,
351
Effect of purification method of β-chitin from squid pen on the properties of β-chitin
352
nanofibers, Int. J. Biol. Macromol. 91 (2016) 987–993.
353
https://doi.org/10.1016/j.ijbiomac.2016.06.060.
354
[15]
S. Ifuku, K. Yamada, M. Morimoto, H. Saimoto, Nanofibrillation of dry chitin powder
355
by star burst system, J. Nanomater. 2012 (2012) 645624.
356
https://doi.org/10.1155/2012/645624.
357
358
[16]
S. Suenaga, K. Totani, Y. Nomura, K. Yamashita, I. Shimada, H. Fukunaga, N.
Takahashi, M. Osada, Effect of acidity on the physicochemical properties of α- and β15
359
chitin nanofibers, Int. J. Biol. Macromol. 102 (2017) 358–366.
360
https://doi.org/10.1016/j.ijbiomac.2017.04.011.
361
[17]
S. Suenaga, M. Osada, Systematic dynamic viscoelasticity measurements for chitin
362
nanofibers prepared with various concentrations, disintegration times, acidities, and
363
crystalline structures, Int. J. Biol. Macromol. 115 (2018) 431–437.
364
https://doi.org/10.1016/j.ijbiomac.2018.04.082.
365
[18]
S. Ifuku, M. Nogi, K. Abe, M. Yoshioka, M. Morimoto, H. Saimoto, H. Yano,
366
Preparation of chitin nanofibers with a uniform width as α-chitin from crab shells,
367
Biomacromolecules. 10 (2009) 1584–1588. https://doi.org/10.1021/bm900163d.
368
[19]
S. Ifuku, M. Nogi, M. Yoshioka, M. Morimoto, H. Yano, H. Saimoto, Fibrillation of
369
dried chitin into 10-20 nm nanofibers by a simple grinding method under acidic
370
conditions, Carbohydr. Polym. 81 (2010) 134–139.
371
https://doi.org/10.1016/j.carbpol.2010.02.006.
372
[20]
Y. Fan, T. Saito, A. Isogai, Individual chitin nano-whiskers prepared from partially
373
deacetylated α-chitin by fibril surface cationization, Carbohydr. Polym. 79 (2010)
374
1046–1051. https://doi.org/10.1016/j.carbpol.2009.10.044.
375
[21]
J. Brugnerotto, J. Lizardi, F.M. Goycoolea, W. Argüelles-Monal, J. Desbrières, M.
376
Rinaudo, An infrared investigation in relation with chitin and chitosan
377
characterization, Polymer. 42 (2001) 3569–3580. https://doi.org/10.1016/S0032-
378
3861(00)00713-8.
379
[22]
B.M. Min, S.W. Lee, J.N. Lim, Y. You, T.S. Lee, P.H. Kang, W.H. Park, Chitin and
380
chitosan nanofibers: Electrospinning of chitin and deacetylation of chitin nanofibers,
381
Polymer. 45 (2004) 7137–7142. https://doi.org/10.1016/j.polymer.2004.08.048.
382
383
[23]
J. Xu, L. Liu, J. Yu, Y. Zou, Z. Wang, Y. Fan, DDA (degree of deacetylation) and pHdependent antibacterial properties of chitin nanofibers against Escherichia coli,
16
384
385
Cellulose. 26 (2019) 2279–2290. https://doi.org/10.1007/s10570-019-02287-2.
[24]
R. Kose, T. Kondo, Favorable 3D-network formation of chitin nanofibers dispersed in
386
water prepared using aqueous counter collision, Sen’i Gakkaishi. 67 (2011) 91–95.
387
https://doi.org/10.2115/fiber.67.91.
388
[25]
A.K. Dutta, N. Kawamoto, G. Sugino, H. Izawa, M. Morimoto, H. Saimoto, S. Ifuku,
389
Simple preparation of chitosan nanofibers from dry chitosan powder by the star burst
390
system, Carbohydr. Polym. 97 (2013) 363–367.
391
https://doi.org/10.1016/j.carbpol.2013.05.010.
392
[26]
A.K. Dutta, H. Izawa, M. Morimoto, H. Saimoto, S. Ifuku, Simple preparation of
393
chitin nanofibers from dry squid pen β-chitin powder by the star burst system, J. Chitin
394
Chitosan Sci. 1 (2014) 186–191. https://doi.org/10.1166/jcc.2013.1023.
395
[27]
K. Azuma, R. Koizumi, H. Izawa, M. Morimoto, H. Saimoto, T. Osaki, N. Ito, M.
396
Yamashita, T. Tsuka, T. Imagawa, Y. Okamoto, T. Inoue, S. Ifuku, Hair growth-
397
promoting activities of chitosan and surface-deacetylated chitin nanofibers, Int. J. Biol.
398
Macromol. 126 (2019) 11–17. https://doi.org/10.1016/j.ijbiomac.2018.12.135.
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Figure captions
403
Fig. 1. Preparation of deacetylated α-ChNFs.
404
Fig. 2. Effect of NaOH aqueous solution treatment time on DA. (b) Magnified illustration of
405
(a). Deacetylated chitin powder (○), solid residue (□) shown in Fig. 1.
406
Fig. 3. Effect of DA on the weight change of α-chitin.
407
Fig. 4. FT-IR spectra of deacetylated chitin powder with different DAs.
408
Fig. 5. FE-SEM image and width distribution of α-ChNFs at DA = 95%.
409
Fig. 6. FE-SEM images and width distributions of α-ChNFs at DA = 66%.
410
Fig. 7. FE-SEM images and width distributions of α-ChNFs at DA = 35%.
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Fig. 8. Effect of DA on the transmittance and photographs of α-ChNF dispersions.
412
Fig. 9. Effect of DA on the viscosity of α-ChNF dispersions.
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Fig. 10. Model for estimating NF width at different DAs.
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18
415
α-Chitin powder
Deacetylation
Centrifugation and decantation
Deacetylated chitin powder
Acetic acid treatment
Centrifugation and decantation
Solid residue
Supernatant
Water added to adjust concentration
Suspension of chitin powder (1 wt%)
Wet pulverization using
Star Burst
416
417
418
419
420
421
422
423
424
425
426
Chitin nanofiber dispersion (1 wt%)
J. Machida et al.
19
Fig. 1
e of acetylation [%]
100
(a)
80
60
40
20
100
80
60
40
20
100
200
300
400
427
428
429
430
431
432
20
40
60
80
100
J. Machida et al.
20
Fig. 2
Weight change [%]
433
434
435
436
437
438
100
80
60
40
20
30
40
50
60
70
Degree of acetylation [%]
J. Machida et al.
21
Fig. 3
439
Transmittance [-]
DA
95%
60%
47%
35%
26%
4000
440
441
442
443
444
3500
3000
2500
2000
1500
1000
500
Wavenumber [cm-1]
J. Machida et al.
22
Fig. 4
445
30
DA 95%
Ave. 34.1 nm
SD 24.6 nm
1 µm
Frequency [%]
25
20
15
10
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
10 passes
NF width [nm]
446
447
448
449
450
451
J. Machida et al.
23
Fig. 5
452
40
Frequency [%]
DA 66%
1 µm
Ave. 28.4 nm
SD 14.8 nm
30
20
10
0 10 20 30 40 50 60 70 80 90
NF w idth [nm]
1 pass
Frequency [%]
40
1 µm
Ave. 31.1 nm
SD 18.4 nm
30
20
10
2 passes
0 10 20 30 40 50 60 70 80 90
NF w idth [nm]
1 µm
10 passes
453
454
455
456
457
458
Frequency [%]
80
Ave. 18.5 nm
SD 6.8 nm
60
40
20
0 10 20 30 40 50 60 70 80 90
NF w idth [nm]
J. Machida et al.
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Fig. 6
459
80
Ave. 20.3 nm
SD 5.5 nm
Frequency [%]
DA 35%
1 µm
60
40
20
1 pass
Frequency [%]
80
1 µm
50
Ave. 18.6 nm
SD 6.7 nm
60
40
20
2 passes
1 µm
Frequency [%]
80
10 passes
10 20 30 40
NF w idth [nm]
10 20 30 40
NF w idth [nm]
50
Ave. 17.6 nm
SD 5.0 nm
60
40
20
460
461
462
463
464
465
10 20 30 40
NF w idth [nm]
50
J. Machida et al.
25
Fig. 7
466
Transmittance [%]
1 pass
3 passes
10 passes
467
468
469
470
471
472
2 passes
5 passes
80
DA of (10 passes)
35%
95%
60
40
20
25
50
75
100
Degree of acetylation [%]
J. Machida et al.
26
Fig. 8
Viscosity [mPa s]
1 pass
473
474
475
476
477
478
479
4000
3500
3000
2500
2000
1500
1000
500
2 passes
5 passes
10 passes
25
50
75
100
Degree of acetylation [%]
J. Machida et al.
27
Fig. 9
480
DA 100%
34 nm
35%
20 nm
66%
28 nm
Estimated
width
Deacetylated
part
Nondeacetylated
part
Acetic acid and
Star Burst
treatments
481
482
483
484
485
486
487
J. Machida et al.
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Fig. 10
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