Fourier Transform Infrared Spectroscopy and Broadband Dielectric Spectroscopy are combined to trace kinetics of mutarotation in L-fucose. After quenching molten samples down to temperatures between T = 313 K and 328 K, the concentrations of two anomeric species change according to a simple exponential time dependence, as seen by an increase in absorbance of specific IR-vibrations. In contrast, the dielectric spectra reveal a slowing down of the structural (α-) relaxation process according to a stretched exponential time dependence (stretching exponent of 1.5 ± 0.2). The rates of change in the IR absorption for α- and β-fucopyranose are (at T = 313 K) nearly one decade faster than that of the intermolecular interactions as measured by the shift of the α-relaxation. This reflects the fact that the α-relaxation monitors the equilibration at a mesoscopic length scale, resulting from fluctuations in the anomeric composition.

1.
T.
Irie
and
K.
Uekama
,
J. Pharm. Sci.
86
,
147
(
1997
).
2.
K.
Grzybowska
,
M.
Paluch
,
P.
Wlodarczyk
,
A.
Grzybowski
,
K.
Kaminski
,
L.
Hawelek
,
D.
Zakowiecki
,
A.
Kasprzycka
, and
I.
Jankowska-Sumara
,
Mol. Pharmaceutics
9
,
894
(
2012
).
3.
B.
Wang
,
S.
Tchessalov
,
M. T.
Cicerone
,
N. W.
Warne
, and
M. J.
Pikal
,
J. Pharm. Sci.
98
,
3145
(
2009
).
4.
J. F.
Carpenter
,
M. J.
Pikal
,
B. S.
Chang
, and
T. W.
Randolph
,
Pharm. Res.
14
,
969
(
1997
).
5.
E.
Kaminska
,
K.
Adrjanowicz
,
K.
Kaminski
,
P.
Wlodarczyk
,
L.
Hawelek
,
K.
Kolodziejczyk
,
M.
Tarnacka
,
D.
Zakowiecki
,
I.
Kaczmarczyk-Sedlak
,
J.
Pilch
, and
M.
Paluch
,
Mol. Pharmaceutics
10
,
1824
(
2013
).
6.
D. J.
Becker
and
J. B.
Lowe
,
Glycobiology
13
,
41R
(
2003
).
7.
V. A.
Yaylayan
,
A. A.
Ismail
, and
S.
Mandeville
,
Carbohydr. Res.
248
,
355
(
1993
).
8.
R. S.
Shallenberger
,
Pure Appl. Chem.
50
,
1409
(
1978
).
9.
M.
Cockman
,
D. G.
Kubler
,
A. S.
Oswald
, and
L.
Wilson
,
J. Carbohydr. Chem.
6
,
181
(
1987
).
10.
D.
Horton
and
Z.
Wałaszek
,
Carbohydr. Res.
105
,
145
(
1982
).
11.
C.
Williams
and
A.
Allerhand
,
Carbohydr. Res.
56
,
173
(
1977
).
12.
A. P.
Dubrunfaut
,
C. R. Acad. Sci.
23
,
38
(
1846
).
13.
F. A.
Carey
,
Organic Chemistry
, 4th ed. (
McGraw-Hill
,
Boston
,
2000
).
14.
E.
Tombari
,
C.
Ferrari
,
G.
Salvetti
, and
G. P.
Johari
,
J. Chem. Phys.
126
,
021107
(
2007
).
15.
N.
Dujardin
,
J. F.
Willart
,
E.
Dudognon
,
F.
Danède
, and
M.
Descamps
,
J. Phys. Chem. B
117
,
1437
(
2013
).
16.
N.
Dujardin
,
J.
Willart
,
E.
Dudognon
,
A.
Hédoux
,
Y.
Guinet
,
L.
Paccou
,
B.
Chazallon
, and
M.
Descamps
,
Solid State Commun.
148
,
78
(
2008
).
17.
S. J.
Angyal
and
V. A.
Pickles
,
Carbohydr. Res.
4
,
269
(
1967
).
18.
D.
Schumacher
and
L. W.
Kroh
,
Food Chem.
54
,
353
(
1995
).
19.
N.
Le Barc'H
,
J.
Grossel
,
P.
Looten
, and
M.
Mathlouthi
,
Food Chem.
74
,
119
(
2001
).
20.
A. E.
Flood
,
M. R.
Johns
, and
E. T.
White
,
Carbohydr. Res.
288
,
45
(
1996
).
21.
A. M.
Silva
,
E. C.
da Silva
, and
C. O.
da Silva
,
Carbohydr. Res.
341
,
1029
(
2006
).
22.
P.
Wlodarczyk
,
K.
Kaminski
,
K.
Adrjanowicz
,
Z.
Wojnarowska
,
B.
Czarnota
,
M.
Paluch
,
J.
Ziolo
, and
J.
Pilch
,
J. Chem. Phys.
131
,
125103
(
2009
).
23.
P.
Wlodarczyk
,
K.
Kaminski
,
S.
Haracz
,
M.
Dulski
,
M.
Paluch
,
J.
Ziolo
, and
M.
Wygledowska-Kania
,
J. Chem. Phys.
132
,
195104
(
2010
).
24.
P.
Wlodarczyk
,
M.
Paluch
,
A.
Grzybowski
,
K.
Kaminski
,
A.
Cecotka
,
J.
Ziolo
, and
J.
Markowski
,
J. Chem. Phys.
137
,
124504
(
2012
).
25.
P.
Wlodarczyk
,
M.
Paluch
,
L.
Hawelek
,
K.
Kaminski
, and
J.
Pionteck
,
J. Chem. Phys.
134
,
175102
(
2011
).
26.
Y.
Wang
,
P.
Wlodarczyk
,
A. P.
Sokolov
, and
M.
Paluch
,
J. Phys. Chem. B
117
,
1475
(
2013
).
27.
P.
Wlodarczyk
,
A.
Cecotka
,
K.
Adrjanowicz
,
K.
Kaminski
, and
M.
Paluch
,
J. Phys.: Condens. Matter
25
,
375101
(
2013
).
28.
N.
Dujardin
,
E.
Dudognon
,
J.-F.
Willart
,
A.
Hédoux
,
Y.
Guinet
,
L.
Paccou
, and
M.
Descamps
,
J. Phys. Chem. B
115
,
1698
(
2011
).
29.
F.
Kremer
and
A.
Schönhals
,
Broadband Dielectric Spectroscopy
(
Springer
,
2003
).
30.
R.
Casalini
,
S.
Corezzi
,
A.
Livi
,
G.
Levita
, and
P. A.
Rolla
,
J. Appl. Polym. Sci.
65
,
17
(
1997
).
31.
G. P.
Johari
,
J. G.
McAnanama
, and
D. A.
Wasylyshyn
,
J. Chem. Phys.
105
,
10621
(
1996
).
32.
B. D.
Fitz
and
J.
Mijovic
,
J. Phys. Chem. B
104
,
12215
(
2000
).
33.
Z.
Wojnarowska
,
P.
Wlodarczyk
,
K.
Kaminski
,
K.
Grzybowska
,
L.
Hawelek
, and
M.
Paluch
,
J. Chem. Phys.
133
,
094507
(
2010
).
34.
Z.
Wojnarowska
,
M.
Paluch
,
P.
Wlodarczyk
,
M.
Dulski
,
R.
Wrzalik
, and
C. M.
Roland
,
J. Phys. Chem. Lett.
3
,
2288
(
2012
).
35.
P.
Griffiths
and
J. A. d.
Haseth
,
Fourier Transform Infrared Spectrometry
, 2nd ed. (
Wiley-Interscience
,
2007
).
36.
S.
Havriliak
and
S.
Negami
,
J. Polym. Sci., Part C: Polym. Symp.
14
,
99
117
(
1966
).
37.
W.
Kossack
,
K.
Adrjanowicz
,
M.
Tarnacka
,
W. K.
Kipnusu
,
M.
Dulski
,
E. U.
Mapesa
,
K.
Kaminski
,
S.
Pawlus
,
M.
Paluch
, and
F.
Kremer
,
Phys. Chem. Chem. Phys.
15
,
20641
(
2013
).
38.
M.
Avrami
,
J. Chem. Phys.
9
,
177
(
1941
).
39.
M. C.
Weinberg
,
D. P.
Birnie
 III
, and
V. A.
Shneidman
,
J. Non-Cryst. Solids
219
,
89
(
1997
).
40.
R. L.
Leheny
and
S. R.
Nagel
,
Phys. Rev. B
57
,
5154
(
1998
).
41.
P.
Lunkenheimer
,
R.
Wehn
,
U.
Schneider
, and
A.
Loidl
,
Phys. Rev. Lett.
95
,
055702
(
2005
).
42.
P.
Lunkenheimer
,
R.
Wehn
, and
A.
Loidl
,
J. Non-Cryst. Solids
352
,
4941
(
2006
).
43.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
 et al, Gaussian 09, Revision A.1, Gaussian Inc., Wallingford, CT,
2009
.
44.
At
$T_{\protect \text{eq}}$
Teq
several effects are observed in the T-dependent BDS and FTIR data. The interested reader is referred to the molecular dynamics section of Ref. 37.
45.
This activation energy roughly agrees with
$E_{\protect \text{a}}=124\pm 9$
Ea=124±9
kJ/mol, as estimated earlier by some of us.27 
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