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Accepted Manuscript
Raman spectroscopy of Bisphenol ‘S’ and its analogy with Bisphenol ‘A’ uncovered
with a dimensionality reduction technique
Ramzan Ullah, Xiangzhao Wang
PII:
S0022-2860(18)30968-2
DOI:
10.1016/j.molstruc.2018.08.025
Reference:
MOLSTR 25546
To appear in:
Journal of Molecular Structure
Received Date: 4 May 2018
Revised Date:
4 August 2018
Accepted Date: 7 August 2018
Please cite this article as: R. Ullah, X. Wang, Raman spectroscopy of Bisphenol ‘S’ and its analogy
with Bisphenol ‘A’ uncovered with a dimensionality reduction technique, Journal of Molecular Structure
(2018), doi: 10.1016/j.molstruc.2018.08.025.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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Raman Spectroscopy of Bisphenol ‘S’ and its analogy with Bisphenol ‘A’
uncovered with a dimensionality reduction technique
Ramzan Ullah a, b, Xiangzhao Wang a, b, *
a
Laboratory of Information Optics and Optoelectronic Technology, Shanghai Institute of Optics and Fine
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Mechanics, Chinese Academy of Sciences, Shanghai 201800, China
b
University of Chinese Academy of Sciences, Beijing 100190, China
*
Corresponding author: wxz26267@siom.ac.cn
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Abstract: Bisphenol ‘S’ (BPS), a frequent substitute of Bisphenol ‘A’ (BPA) which is prohibited in specific applications because of
its toxicity, is investigated by Raman spectroscopy (150 cm-1 to 3600 cm-1). Observed scattering peaks are assigned by Density
Functional Theory (DFT) calculations. Principal Component Analysis is utilized to search for correlating molecular vibrations of
BPA and BPS. Raman spectra provide new intuitions like C-H stretching vibrations in addition to reinforcing some of the
previously reported correlation results from FTIR spectroscopy of BPA and BPS. List of frequencies is populated illustrating the
association between BPA and BPS by means of their corresponding molecular vibrations aiding in classifying as well as exploring
the culprit behind their toxicity.
Keywords: Raman Spectroscopy; Inelastic scattering including Raman; Lasers; Bisphenol “A”, BPA; Bisphenol “S”, BPS; Principal Component
Analysis, PCA.
1. INTRODUCTION
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Raman effect, a type of light-matter interaction, discovered by Professor
C.V. Raman and K. S. Krishnan, was reported in 1928 [1, 2]. Spectroscopic
analysis of Raman effect called Raman spectroscopy is the study of the
interaction between light and matter in which the light or laser is
inelastically scattered. C.V. Raman reported the effect that approximately 1
out of a million photons is dispersed in an inelastic manner. This was a
groundbreaking discovery. In Raman scattering, When the photon is
incident upon the matter, it interacts with it resulting in shifting of its
wavelength to either higher or lower end. Increase in wavelength which is
usually termed as a Redshift of photons is widespread which is subject to
"Stokes shift". When electron cloud of the functional groups encounters
incident photons, electrons are excited to virtual states. When electrons are
excited by incident photons, some energy of the photons is lost as phonon
energy and ultimately detected as Stokes Raman scattering. This loss of
energy is attributed to the structure of the molecule, functional group, and
types of atoms, etc. So, it carries vibrational information of a molecule just
like infrared spectroscopy but works on a different principal. Raman
scattering intensity is different for different molecules and functional
groups. It is, heavily dependent on the polarization state of the molecule [3].
If a change in polarizability of the molecule is larger, then the intensity will
be higher as well. So, if a molecule has a vibrational transition which has
very low polarizability associated with it, it will not be Raman active and
will not appear in the Raman spectra. In infrared active modes, electric
dipole moment, matters and in Raman active modes, polarizability plays a
pivotal role [4]. This is the reason Infrared spectroscopy, and Raman
spectroscopy are considered complementary [5]. Infrared and Raman
spectroscopy have been utilized in tremendous applications covering
diverse areas of research [6-18].
Bisphenol “A” (BPA), a widespread environmental hormone, has been
produced on a mass scale by the plastic industry since its inception [19].
Due to its unique features, BPA plays a key role in many applications
mostly related to plastic and epoxy resin [20, 21]. Disposable as well as
reusable food and drink canisters or bottles are made of polycarbonate
plastic whose main component is BPA and epoxy resin made of BPA, is
used to line the inner walls of the containers [22]. BPA based plastic is
frequently used in compact discs, eyeglasses, sunglasses, possibly contact
lenses, protective equipment for sports, water pipes and virtually anything
made of plastic. BPA is present in medical devices and dental sealants [23].
Cash register receipts printed by ATM and other similar devices on thermal
paper contain BPA coating [24-26]. Various daily life products like soaps,
lotions, shampoo, detergents, etc. may contain BPA [27]. With increasing
number of reports about the ill health effects of BPA, restrictions by the
relevant agencies on BPA usage and anxiety in public on this issue, plastic
products with a label “BPA Free” are gradually dominating the market
mostly at a high cost [28, 29]. However, the fact behind “BPA Free” label is
rather disappointing. It may not be the case with all, but some of the
manufacturers have replaced BPA with its derivatives like Bisphenol “S”
(BPS) and others [30-34]. Having similar molecular structure like BPA,
BPA substitutes including BPS show similar toxic behavior [35-41]. BPS,
an ideal replacement of BPA, has similar applications as BPA.
BPS has recently come into the limelight as an alternate of BPA. BPA is a
toxic and possible carcinogen material used in food contact products and is
banned now in many countries for such purpose. One aftermath of the
prohibition on BPA was the use of BPS alternatively to bypass the law.
BPS has the same level of estrogen mimicry and hormonal activities like
BPA[31, 42-60]. Health agencies need substantial evidence in this respect to
put it under restriction which might take years to get., Even after the
interdiction on BPS, manufacturers would like to move to the next
derivative of BPA which fulfills the purpose. BPS has been investigated by
FTIR spectroscopy with various absorption bands assigned, and similar
bands between BPA and BPS were reported [61]. FTIR and Raman studies
are correlative to each other. The picture is not complete without Raman
spectroscopy of BPS. We present here the Raman spectroscopy of BPS and
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although there are total 8 C-H stretching vibrations in the molecule of BPS.
Similarly, there are two O-H stretching vibrations which are not observed
here. After C-H stretching vibrational region, there is no peak until
approximately1700cm-1.
Experimental Raman and simulated spectra of BPS in the range 750-1700
cm-1 is presented in Fig. 3. There are two sharp spikes observed from the
right side in the experimental spectra. B3LYP also suggest two peaks very
close to each other making a V like shape. B3LYP shows the right branch
higher in intensity than the left branch, but in the experimental spectra, two
branches have the same intensity. However, seeing the horizontal axis, there
is no other peak to the right, these peaks are assigned in the same order. So,
1601.95 cm-1 is assigned to two simulated peaks of 1637.24, and 1637.59
cm-1 and their frequency values are also suggesting that they would appear
like one peak in the spectra. These two peaks are from the active C-C
stretching in the rings. Similarly, the second branch of the peak, 1584.42
cm-1 is attributed to two simulation peaks of 1621.69 and 1624.96 cm-1 and
once again motions are same in these peaks too, active C-C stretching in the
rings in different fashions. BPS is a relatively small molecule; its Raman
spectra is not overcrowded with vibrational peaks. Next is a low-intensity
peak at 1503.3 cm-1 which makes pair simultaneously with 1528.87 and
1527.59 cm-1 which are appearing as one peak. Kindred vibrations are
involved in these modes in which hydrogen atoms attached to the rings are
moving side to side along the plane of the rings causing C-C stretching in
both the rings which in turn propagating 6C and 7C stretching to and from
1S in addition to 16C-4O and 17C-5O stretching. A similar peak having
low intensity at 1287.96 cm-1 is pairing to two calculated peaks of 1290.64
and 1287.10 cm-1 visible in Fig. 3 as a single peak at 1291 cm-1.
Surprisingly, this peak involves the same type of vibration as 1503.3 except
6C and 7C stretching to and from 1S which is absent in this mode.
Figure 1. BPS Molecule along with label numbers.
2. Experimental and Simulation Procedures
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3. Results and Discussion
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The exciting laser frequency for Raman spectra was 532 nm, and the same
frequency was used in simulations too, to get the optimum results. One of
the major advantages of Raman spectroscopy is no sample preparation. Our
samples were in powder form. Xplora Raman system was used to take the
measurements [51]. Raman spectra were recorded from 150 cm-1 to 3600
cm-1 which are shown in Fig. 2, 3 and 4 truncated for clarity in the absence
of scattering peaks. Calculations associated with Density Functional Theory
(DFT) were implemented by Gaussian 09 [64] alongside two functionals
labeled as B3LYP and WB97XD. 6-311G basis set conjointly with (3df,
3pd) polarization and ++ diffuse functions were exploited in both B3LYP
and WB98XD computations [65]. It is observed that B3LYP is achieving
superior prediction of the experimental values than of WB97XD having
empirical dispersions. Solely B3LYP spectra are delineated jointly with
experimental spectra in figure 2, 3 and 4 while Table. 1 should be consulted
for corresponding values of WB97XD. List of calculated frequencies
presented in Table. 1 is the same as reported earlier [61], however, the
intensity profile and experimental values are Raman active modes. Due to
limited computational resources, gas phase calculations were done which is
obviously a crude approximation of experimental Raman spectra. VEDA is
put to work for Potential Energy Distribution (PED) of every DFT
computed frequency mode furnished in Table. 1 [66]. Experimental and
simulation spectroscopic data both for BPA and BPS is available in the
supplementary material.
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its correlation with BPA to have a complete picture of the situation. A
molecule of BPS is shown in Figure 1. Three-dimensional molecular
structures of BPS and BPA are available by ChemSpider for viewing and
exploring further [62, 63].
A. BPS Raman Spectra Interpretation
Experimental Raman and Simulated Raman spectra of BPS in the range
3000 – 3300 cm-1 is shown in Figure. 2. Assignments of observed
experimental scattering peaks are given in Table. 1. This region is entitled as
O-H (rightmost) and then C-H stretching vibrations. Raman spectra do not
present O-H stretching vibrations, and such vibrations are seen in the
infrared spectra instead. In experimental Raman spectra of BPS in Figure. 2,
there is a sharp peak which is obviously from C-H stretching vibrations.
This sharp peak has two more sharp branches making a V like shape. So,
the one peak of 3072. 6 cm-1 is assigned to 3195.58 cm-1 and 3195.66 cm-1
which come from the stretching of 20H-10C, 24H-14C, 25H-15C and 21H11C and they have a different pattern of vibration in each mode. The second
branch is at the frequency of 3070.24 cm-1 and is assigned to two calculated
vibrational frequencies of 3164.05 and 3164.15 cm-1, and both originate
from the stretching of hydrogen atoms attached to the rings. There are no
other C-H stretching vibrations observed in experimental Raman spectra
Figure 2. Experimental and Calculated (B3LYP) Raman Spectra of BPS in
the range 3000-3300 cm-1 dominated by C-H stretching vibrations. * means
multiple peaks are buried under one peak. Consult Table. 1 for detail.
Frequency values are rounded to whole numbers.
Some little peaks can be seen in the experimental spectra of BPS in Fig. 2
just before the 1139.07 cm-1 peak. These peaks are ignored to avoid any
misinterpretation due to low signal to noise ratio. 1139.07 cm-1 is assigned
to 1161.13 cm-1. 1139.07 cm-1 is caused by 7C-1S-6C symmetric stretching
along with symmetric stretching of 2O-1S-3O. Scattering peaks at 1104.03
and 1073.6 cm-1 are straightforward to appoint with 1107.66 and 1084.39
cm-1 respectively. Similar motions are occurring in these modes like the
previous mode but in slightly different manner. 1104.03 is originated by
asymmetric stretching of 7C-1S-6C while 1073.6 cm-1 has symmetric
stretching of 7C-1S-6C and 2O-1S-3O.
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Figure 3. Experimental and Calculated (B3LYP) Raman Spectra of BPS in
the range 750-1700 cm-1. * means multiple peaks are buried under one
peak. Consult Table. 1 for detail. Frequency values are rounded to whole
numbers.
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all the calculated scattering peaks including the ones for which no
experimental peak was observed, is available in the supplementary section
along with critical parameters obtained from DFT calculations like point
group and energy, etc. Similarly, animated pictures of BPS molecule
corresponding to all the calculated frequencies (B3LYP) given in Table 1
are also available in supplementary material.
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An experimental peak of 834. 449 cm-1 accompanied by a low-intensity
peak at 814.371 near its foot is assigned to 837.92 and 842.22 cm-1, while
814.371 is assigned to 828.49 and 826.56 cm-1. Origin of motion in 834.449
is C-C bending in the rings with variations while in 814.371 is HCCC
torsion due to up and down motion of hydrogen atoms connected to the
rings.
Experimental and calculated Raman spectra of BPS in the range 150-750
cm-1 is shown in Fig. 4. Intensity profile is evident to accredit the
experimental peaks at 646.266 and 632.486 cm-1. 646.266 cm-1 is obviously
designated to 685.80 cm-1 calculated peak. It is because of 6C-1S-7C
stretching and out of plane bending of 2O-1S-3O along with the rings.
Similarly, the experimental peak at 632.486 cm-1 is attributed to 641.51,
644.87 and 647.72 cm-1 and these peaks are the results of C-C bending in
the rings causing distortion and S-C stretching. 557.932 cm-1 is ascribed to
multiple peaks of 566.70 and 557.52 cm-1. 2O-1S-3O and 6C-1S-7C
bending and wagging of hydrogen atoms on the rings are responsible for
these modes. The experimental peak at 507.175 cm-1 is not in good shape. It
was hard to take the value of this peak. The highest point of the peak
(507.175 cm-1) is at this moment reported. According to the intensity
profile, 510.98 and 506.61 cm-1 are imputed to the experimental peak at
507.175 cm-1. Out of plane bending of carbon atoms in the rings is common
in both vibrations. 510.98 cm-1 has an additional contribution from 2O-1S3O bending. 379.484 is deputized effortlessly to 391.00, 388.93 and 386.73
cm-1 which are appearing as a single peak in the calculated spectra. 391.00
cm-1 is due to rocking of 5O and 4O parallel to the plane of the respective
rings. 388.93 and 386.73 cm-1 are propagated by wagging of 26H and 27H
perpendicular to the plane of the rings. 374.111 cm-1 is nominated to 376.09
cm-1 which has wagging of 26H and 27H perpendicular to the plane of the
rings with extra scissoring of 7C-1S-6C. 293.023 cm-1 is assigned to 274.79
cm-1 and vibration is like both the rings are stretching out and in across the
central S atom. 276.693 cm-1 is assigned to 269.64 cm-1 which is comprised
of out of plane bending of carbon atoms in the rings. 190.798 cm-1
experimental peak is attached to 182.42 calculated peak, and DFT analysis
shows that bending of 6C-1S-7C is liable for this mode. Motion is as if two
rings are vibrating in the partial rotation along the line passing through the
center of the ring. 172.389 cm-1 affixed to 162.26 cm-1 is associated with
6C-1S-7C bending and up-down motion of oxygens fastened to the rings.
All the observed Raman scattering peaks of BPS have been assigned in the
Table. 1 along with PED analysis showing precisely the nature of motions
involved. Table. 1 shows only those calculated scattering frequencies
which have been assigned with the experimental frequencies. A full list of
Figure 4. Experimental and Calculated (B3LYP) Raman Spectra of BPS in
the range 150-750 cm-1. * means multiple peaks are buried under one peak.
Consult Table. 1 for detail. Frequency values are rounded to whole
numbers.
Table 1. Assignment table of observed Experimental and
corresponding calculated Raman scattering frequencies of BPS along
with PED. Same color adjacent cells represent multiple assignments.
Bisphenol S (Raman)
Sr. No Raman
Raman
Raman
PED (%) by VEDA
Frequency Frequency Frequency
(cm-1)
(cm-1)
(cm-1)
B3LYP at WB97XD Experiment
532 nm
at 532 nm
al at 532
nm
1. 162.26
164.66
172.389
s51 BEND CSC (22)
s65 TORS CCCC (-19)
2. 182.42
190.19
190.798
s41 BEND CCS (-33)
s48 BEND OSC (15)
s50 BEND SCC (33)
3. 269.64
276.03
276.693
s70 OUT OCOS (-13)
s74 OUT CSCC (-12)
4. 274.79
286.50
293.023
s25 STRE SC (24)
s26 STRE SC (24)
5. 376.09
374.44
374.111
s49 BEND OSO (-13)
s51 BEND CSC (-16)
s63 TORS CCCS (-13)
376.16
379.484 s52 TORS HOCC (48)
6. 386.73
s53 TORS HOCC (48)
7. 388.93
390.21
379.484 s52 TORS HOCC (44)
s53 TORS HOCC (44)
8. 391.00
400.97
379.484
s46 BEND OCC (-26)
s47 BEND OCC (26)
s71 OUT OCCS (-19)
9. 506.61
512.78
507.175
s72 OUT OCCC (19)
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569.03
557.932
12. 566.70
13. 641.51
577.48
648.53
557.932
632.486
651.56
632.486
15. 647.72
658.98
632.486
16. 685.80
699.77
646.266
17. 826.46
836.67
814.371
18. 828.49
838.62
814.371
19. 837.92
851.39
834.449
20. 842.22
856.33
834.449
21. 1084.39
1118.34
1073.6
22. 1107.66
1139.53
1104.03
23. 1161.13
1199.09
1139.07
24. 1287.10
1318.83
1287.96
25. 1290.64
1322.42
1287.96
26. 1527.59
27. 1528.87
28. 1621.69
1554.53
1555.88
1656.66
B. Principal Component Analysis
A simple introduction to Principal Component Analysis (PCA) is
reproduced for self-consistency. PCA is a dimensionality reduction
technique mostly used to classify entities. PCA is used to search for
correlating frequencies between BPS and BPA in this work. Raman spectra
of BPA was computed with identical method and system as BPS. PCA
analysis is performed, and two Principal Components (PCs) are determined.
Due to a limited number of data sets, complete information is enclosed by
PC1 as shown in Figure. 5 and 6. BPA spectra are plotted with PCs to
acquire the matching frequencies of the two materials. Matching areas are
marked in Fig. 5 and 6. Whole spectra are truncated into two for clarity.
PCA reduces the number of dimensions in a large data set. It constructs
small blocks of information called Principal Components (PCs) out of a
massive data. These Principal Components are marked as PC1, PC2, and
PC3, etc. Every principal component bears a fraction of all the information
together. PC1 comprises of the highest fragment of the information. It
declines with subsequent PCs. It is resolved later how many PCs to consider
for analysis without losing valuable information by examining the scree plot
and elbow point inside it. In the scree plot, principal components are drawn
along with their eigenvalues. BPA spectra are plotted along with PC1 for
easy comparison. One must be extremely cautious while comparing the
PC1 and BPA spectra because PC1 already contains BPA spectra along
with BPS spectra. PCA of BPA and BPS is given in Fig. 5 and 6 in
different ranges. 12 regions are determined where the matching is prevalent.
Experimental Raman spectra of BPA and BPS are then displayed in Fig. 7,
8 and 9 to identify those vibrational peaks.
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14. 644.87
STRE CH (-14) s9
STRE CH (36) s10
STRE CH (36)
STRE=Stretch (ν), TORS=Torsions (τ), OUT=Out of plane bending (γ),
BEND=Bending (δ), s#= identity number, s13 STRE CC ≠ s14 STRE
CC, means C-C stretching is happening on different atoms in that
molecule.
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11. 557.52
s73 OUT OCCC (-19)
s49 BEND OSO (42)
s72 OUT OCCC (11)
s73 OUT OCCC (11)
s49 BEND OSO (-20)
s51 BEND CSC (12)
s70 OUT OCOS (-31)
s25 STRE SC (-12)
s26 STRE SC (-12)
s27 BEND CCC (14)
s28 BEND CCC (14)
s42 BEND CCC (18)
s43 BEND CCC (18)
s42 BEND CCC (-18)
s43 BEND CCC (18)
s25 STRE SC (-11)
s26 STRE SC (11)
s70 OUT OCOS (13)
s54 TORS HCCC (12)
s55 TORS HCCC (12)
s58 TORS HCCC (23)
s59 TORS HCCC (23)
s54 TORS HCCC (-12)
s55 TORS HCCC (12)
s58 TORS HCCC (-24)
s59 TORS HCCC (24)
s44 BEND CCC (17)
s45 BEND CCC (17)
s44 BEND CCC (16)
s45 BEND CCC (-16)
s17 STRE CC (12)
s18 STRE CC (12)
s23 STRE SO (-12)
s24 STRE SO (-12)
s13 STRE CC (-10)
s14 STRE CC (10)
s17 STRE CC (-13)
s18 STRE CC (13)
s23 STRE SO (-31)
s24 STRE SO (-31)
s21 STRE OC (26)
s22 STRE OC (-26)
s21 STRE OC (27)
s22 STRE OC (27)
s19 STRE CC (16)
s20 STRE CC (16)
s19 STRE CC (-16)
s20 STRE CC (16)
s11 STRE CC (11)
s12 STRE CC (11)
s11 STRE CC (10)
s12 STRE CC (-10)
s13 STRE CC (-11)
s14 STRE CC (11)
s7 STRE CH (-48) s8
STRE CH (49)
s7 STRE CH (49) s8
STRE CH (48)
s5 STRE CH (14) s6
STRE CH (-14) s9
STRE CH (-35) s10
STRE CH (36)
s5 STRE CH (-14) s6
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10. 510.98
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1503.3
1503.3
1584.42
29. 1624.96
1660.52
1584.42
30. 1637.24
1675.90
1601.95
31. 1637.59
1676.46
1601.95
32. 3164.05
3192.88
3070.24
33. 3164.15
3192.98
3070.24
34. 3195.58
3215.73
3072.6
35. 3195.66
3215.79
3072.6
Figure 5. PCA analysis of Raman Spectra of BPS and BPA. As there is no
information in PC2, Relevant molecules are given there for comparison.
Arrows are showing the critical regions of frequencies. Exact frequencies
are given in Table. 2.
12 frequencies are diagnosed and listed in Table. 2 which are having a
connection. Fig. 7 is showing the spectra of BPA and BPS in the range
3000 to 3200 cm-1. This region is monopolized by C-H and O-H stretching.
Due to the nature of FTIR and Raman spectroscopy, O-H stretching is
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BPA, out of plane bending of C-C-C in both the rings is prevailing.
Hydrogen atoms are wagging side-by-side in BPS but up-down in BPA.
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clearly observed in FTIR spectra while C-H vibrations are seen distinctly in
Raman spectra. BPS is manifesting two peaks at 3073 and 3070 cm-1 in Fig.
7. BPA is showing a single peak around this location at 3068 cm-1. This
mode was missing in the comparative study of FTIR of BPS and BPA
reported earlier [61]. Instead, O-H stretching was described in FTIR
spectroscopy of BPS and BPA which is missing here [61]. This region is
vital for classification because it is not crowded by different vibrational
motions owing to ambiguity. The relevant PED analysis for these vibrations
in Table. 1 illustrates further that these vibrations are purely from C-H
stretching. Interestingly, in the FTIR spectroscopy of BPS and BPA, BPS
was displaying two peaks but BPA, only one peak for O-H stretching
vibrations. Same is the case here; BPS is exposing two peaks while BPA
only one for C-H stretching.
Figure 7. Comparison of Raman Spectra of BPA and BPS (3000-3200 cm) with the frequencies of interest marked according to PCA analysis. The
dotted line is the zero-reference line for BPA spectra.
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Figure 6. PCA analysis of Raman Spectra of BPS and BPA in the range
2700-3300 cm-1. Arrow is showing the critical region of frequencies. Exact
frequencies are given in Table. 2.
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Experimental Raman spectra in the range 750 to 1700 cm-1 of BPA and
BPS is shown in Fig 8 where the arrows are showing those frequencies
which have been identified by PCA given in Fig. 5. Table 2 indexes these
frequencies and type of motions can be seen in the respective visualization.
Few frequencies are reinforcing
the previously reported FTIR
spectroscopic vibrations of BPS and BPA [61]. For example, frequencies at
serial number 10 and 11 (Table. 2) are bolstering the FTIR absorption
frequencies of BPA (1599 & 1612 cm-1) and BPS (1585 & 1603 cm-1).
Two vibrations of BPS (1104 and 1139) are related to one frequency of
BPA at 1115 cm-1 because of the existence of only one peak of BPA in the
vicinity. A similar interaction was addressed for 1101 cm-1 (BPA) and 1103
cm-1 (BPS) in the FTIR spectroscopy of BPS and BPA. Assignment of
1115 with 1139 seems unfit in this context. Assignment specifically for
these peaks was challenging in the FTIR spectroscopy. The relative
assignment with Raman spectroscopy seems right in contrast to FTIR
spectroscopic study primarily in the case of 1104 (BPS Raman) in
comparison to 1103 (BPS FTIR) cm-1. Pair of 833 (BPA) and 834 (BPS)
has the similar role with 827 (BPA) and 837 (BPS) of corresponding FTIR
spectroscopy. Combination of 819 (BPA) and 814 (BPS) which was
clouded in FTIR spectroscopy, is vividly illustrating the shaking of
hydrogen atoms hooked up with the rings. Raman spectra of BPS and BPA
is illustrated in Fig. 9 from 150 to 750 cm-1. Serial number 5 and 6 of Table.
2 are uncovering new insights of distortion in the rings. A couple of
frequencies at serial number 4 (Table. 2) are restating the 563 (BPA) and
557 (BPS) of FTIR spectroscopy. The situation is somehow the same in this
matter. There is a slight difference in the motions of these molecules. In the
case of BPS, stretching across the central joining atom is prevalent while in
BPA, it is bending. Similarly, in BPS, C-C stretching is extensive while in
Frequencies at serial number 3, and 2 of Table. 2 appear as a couple where
379 cm-1 is higher than 374 cm- in intensity. The same pattern at 388 and
385 cm-1 is viewed in the corresponding BPA spectra. The experimental
peak of 379 for BPS has three possible assignments with DFT calculated
peaks detail of which is given in Table. 1. However, the assignment with
391 cm-1 seems the only correct assignment when comparing with BPA
spectra. Usually, such low-intensity peaks are ignored first due to low
signal to noise ratio and second because of worse detection limit. However,
the unique pattern makes it unignorable. Pair of 284 and 293 cm-1 for BPA
and BPS respectively are connecting these materials with congruous
vibrations in the rings.
Figure 8. Comparison of Raman Spectra of BPA and BPS (750-1700 cm-1)
with the frequencies of interest marked according to PCA analysis. The
dotted line is the zero-reference line for BPA spectra.
Raman scattering in BPA and BPS once again exposes the role of benzene
rings in connecting the materials based on molecular vibrations. Raman
spectroscopy not only reinforces the FTIR spectroscopic frequencies of
ACCEPTED MANUSCRIPT
11
1619
1602
12
3068
3070
3073
supplementary materials
See “Visualization 11” in the
supplementary materials
See “Visualization 12” in the
supplementary materials
4. Conclusion
RI
PT
Raman spectra (150 cm-1 to 3600 cm-1) of BPS is exhibited, and molecular
vibrations are imputed as per DFT calculations. Raman scattering peaks
have been deliberated in detail and their pertinent vibrations too. Raman
spectra reinforce the previous FTIR spectroscopy of BPS and BPA and add
new acumens specially C-H stretching in the list. PCA is availed to explore
the connection between BPS and BPA by means of their molecular
vibrations. Twelve pairs of frequencies are determined to advocate the
engagement of benzene rings which are not only classifying them in a
group but may also have some clue towards the origin of their toxicology or
carcinogenicity.
SC
BPS and BPA but also provides some new vibrations which were absent in
FTIR spectroscopic analysis specially C-H stretching. Reinforcement of
FTIR frequencies does not mean the same vibrational mode, but it indicates
that similar vibrations are involved in corresponding frequencies. It is very
well clear from the studies of BPA and BPS that benzene rings are of
importance in the similarity among their molecular vibrations. Rest of the
structure especially between the rings does not have much influence on the
correlation. It is of no surprise that many such structures are toxic. It is an
ideal situation to use machine learning techniques to detect these materials
in mixtures. Machine learning algorithms can classify them very well. By
exploiting the structure of these molecules, it should be possible to change
their toxic behavior. A similar structure called EPI-001 is being assessed for
treating prostate cancer [67].
Acknowledgment
M
AN
U
This work was supported by Chinese Academy of Sciences, President’s
International Fellowship Initiative, Grant No. (2017PB0041) and National
Science and Technology Major Project of China, Grant No.
(2017ZX02101006).
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1.
2.
TE
D
Figure 9. Comparison of Raman Spectra of BPA and BPS (150-750 cm-1)
with the frequencies of interest marked according to PCA analysis. The
dotted line is the zero-reference line for BPA spectra.
AC
C
EP
Table 2. Identified molecular vibrations of BPA and BPS by PCA
analysis along with the nature of motion involved.
Sr.
BPA
BPS (cmMotions involved (DFT Calculations)
-1
1
No
(cm )
)
1
284
293
See “Visualization 1” in the supplementary
materials
2
385
374
See “Visualization 2” in the supplementary
materials
3
388
379
See “Visualization 3” in the supplementary
materials
4
565
558
See “Visualization 4” in the supplementary
materials
5
641
632
See “Visualization 5” in the supplementary
materials
6
650
646
See “Visualization 6” in the supplementary
materials
7
819
814
See “Visualization 7” in the supplementary
materials
8
833
834
See “Visualization 8” in the supplementary
materials
9
1115
1104
See “Visualization 9” in the supplementary
(1139
materials
Tentative)
10
1600
1584
See “Visualization 10” in the
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Highlights
1. Raman (150 cm-1 to 3600 cm-1) spectra of Bisphenol ‘S’
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2. DFT simulations in conjunction with experimental Raman spectra of BPS.
3. Interpretation of observed Raman scattering peaks of BPS.
4. Comparison with Raman spectra of Bisphenol ‘A’
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5. Finding correlating Raman scattering frequencies of BPA and BPS
6. Reinforcement of Raman modes toward IR modes of BPA and BPS
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7. Role of benzene rings in linking BPA and BPS and possibly in toxicity
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