Supplementary Material (SM)

Photocatalytic degradation of tetracycline antibiotic by BaWO 4 microcrystals

with surface modified by silver nanoparticles
V.L.G. Cruz1, A.J.P. Silva Neto1, B.S. Sousa2, P.B. de Sousa2, E.P. Ribeiro1, S.F.L Quinzeiro1, F.H.P.
Lopes1, G.O.M. Gusmão1, R.R.P. Garcia3, L.S. Cavalcante1,2*
1
CETEM-GERATEC-PPGQ, Universidade Estadual do Piauí—UESPI, Rua: João Cabral, N. 2231, P.O. Box 381, 64002150, Teresina-PI, Brazil
2
PPRPG-PPGCM, Universidade Federal do Piauí—UFPI, Bairro Ininga, 64049-550 Teresina, PI, Brazil
3
Universidade Federal Rural de Pernambuco, Rua: 173,300, Garapu, Unidade Acadêmica do Cabo de Santo Agostinho, Cabo de Santo Agostinho, PE, Brazil

* Mob: +55 86 99412 1001. Email address: [email protected] (L.S. Cavalcante)

Preprint revised version 3 to Surfaces and Interfaces December 28, 2024

Experimental details

Characterizations

The structural analysis of pristine BaWO 4 crystal and BaWO4 microcrystals/x.AgNPs at

proportions (x = 1, 2, and 4% at mass) was conducted using X-ray diffraction (XRD). The X-ray

diffractometer model DRX 6000 from Shimadzu®, Japan, was utilized to obtain the XRD patterns of

the samples. It operated at 40 kV and 30 mA, using Cu-Kα radiation with a wavelength (λ) of 1.5406

Å. The scan range was 10 to 110° with a rate of 2°/min. Raman spectroscopy analyses were performed

in a Senterra II microspectrometer (Bruker®, Germany) using a laser with λ max = 785 nm as an

excitation source, an output power of 100 mW, the spectral resolution of 3 cm -1, and the range from 50

to 1,000 cm-1. Before preparing four thin pellets, we used an analytical balance to weigh approximately

1 mg of each sample and 100 mg of potassium bromide (KBr) as a standard used on the background.

The solid samples (crystals/KBr) were homogenized into fine powders using a high-friction-resistant

mortar and pestle with several grinding cycles. Subsequently, Fourier transform infrared (FT-IR)

spectra were measured in a model IRPrestige-21 spectrometer (Shimadzu® Japan) in a range from 400

to 1,200 cm-1 collected with 150 scans and a resolution of 2 cm -1. Scanning electron microscopy (SEM)

images were obtained using a field emission electron microscope JEOL JSM-7401F at an acceleration

i
tension of 5.0 kV, a secondary electron image detector, a working distance ranging from 3.0 mm, and a

resolution of 1.5 nm. The UV–vis spectra were obtained using a spectrophotometer model 2600

(Shimadzu®, Japan), scanning in the range of 200 to 800 nm and set to the diffuse reflectance mode.

For these powder measurements, a specific sample holder was used. Barium sulfate (BaSO 4) served as

the standard reference material to achieve maximum reflectance.

Photocatalytic assays

In this study, we synthesized pristine BaWO4 microcrystals and modified BaWO4 microcrystals

with different amounts of AgNPs (x = 1, 2, and 4% at mass) using the Ion Injection in Hot Solution

with Fast Cooling (IIHSFC) method at 90 °C for 30 seconds. The aim was to investigate their

photocatalytic properties for degrading the TC antibiotic (C 22H24N2O8, molar mass: 444.440 g/mol)

under UV-C lamp irradiation (OSRAM® brand, 15 W, λ max = 254 nm ≈ 4.88 eV). We conducted a

concentration test using different amounts of BaWO 4 microcrystals (25 mg, 50 mg, 75 mg, 100 mg) in

varied volumes of TC solution (25, 50, 75, 100 mL, 1×10 -5 mol/L). Each catalyst was evaluated at all

volumes. The samples were prepared by mixing the microcrystals and the antibiotic solution using an

ultrasonic bath (TABLETOP 402 DIGITAL, Delta® Ultrasound). Before each irradiation, the mixture

was stirred without light for 30 minutes to achieve adsorption-desorption equilibrium. We then

subjected these mixtures to UV-C lamp irradiation, and collected 2.2 mL aliquots at intervals of 10, 20,

40, 50, and up to 240 minutes of light exposure. After each collection, the samples were centrifuged to

separate the catalysts from the liquid phase. UV-Vis spectroscopic analysis was performed to examine

the absorption peaks at λmax ~ 356 nm of TC antibiotic after different exposure times. The degradation

of TC antibiotic over time is expected to vary based on the amount of catalyst and solution volume

used. We then analyzed the results to determine the conditions that resulted in the highest degradation

of TC antibiotic. After completing the tests, we conducted a similar experiment using a 50 mg powder

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of pristine BaWO4 microcrystals and modified BaWO 4 microcrystals with different amounts of

x.AgNPs (x = 1, 2, and 4% at mass) in 75 mL of TC antibiotic solution. This allowed us to investigate

the efficacy of the modified microcrystals in degrading the TC antibiotic and to understand their

photocatalytic properties better. We also subjected the catalyst to photolysis to investigate the effects of

UV-C light on the stability of the molecule, including potential degradation processes. Sample

collection for the catalyst followed the same procedure as in the photocatalysis steps. All experiments

were performed in triplicate.

Scavengers assays

The test for capturing radicals is similar to photocatalysis, in which 50 mg crystals, and 75 mL

of diluted TC antibiotic solution were placed in a beaker. After waiting for 5 min in the dark, the

calculated amount of each scavenger was added to the solution, following specific proportions. The

scavengers included isopropyl alcohol (ISO, C 3H8O, 99.5% purity, Dynamics®) to capture hydroxyl

(OH), p-benzoquinone (BQ, C6H4O2, 98% purity, Dynamics®] to capture superoxide (O2-), ammonium

oxalate (OA, (NH4)2C2O4.H2O, 99% purity, Dynamics®) to capture the holes (h+), and silver nitrate

(AgNO3, 99% purity, Sigma-Aldrich®) to capture the eléctron (e-). The scavenger ratios were

calculated at approximately 1×10-4 mol/L. The procedure allowed for the isolation and analysis of the

distinct effects of each reactive species during the photocatalytic degradation process of TC antibiotic,

as described earlier. All experiments were performed in triplicate.

Rietveld refinement analysis

In our study, we meticulously examined both pristine BaWO 4 microcrystals and modified
BaWO4 microcrystals with varying percentages of AgNPs (x = 1, 2, and 4% at mass). Our findings
reveal that these microcrystals possess a scheelite-type tetragonal structure with a space group (I41/a).
By utilizing the Rietveld refinement method, we accurately determined the atomic positions, lattice
parameters, and unit cell volume of the pristine BaWO 4 microcrystals obtained through the IIHSFC
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method at 90 °C for 30 seconds. Our comprehensive qualitative and quantitative analysis was
conducted using the GSAS-II software (Toby e Von Dreele, 2013) and the Inorganic Crystal Structure
Database (ICSD) with the Crystallographic Information File (CIF) File No. 193493 (Shivakumara et
al., 2015).
The structural refinement quality is generally checked using the R-values (Rexp, RBragg, and Rwp),
χ2, and goodness of fit (S) (Toby, 2006). The Rietveld refinement method (Rietveld, 1969) is based on
the construction of diffraction patterns calculated concerning the structural model employed as a
crystallographic standard (Carruthers e Watkin, 1979). This structural refinement uses the patterns
calculated with a fit of the adjustment with finding pattern data to provide the structural parameters of
the sample and the profile diffraction. The low difference (nearly zero) in the intensity scale between
the observed and calculated patterns is the best way to judge the success of the Rietveld refinement
calculations (Nogueira et al., 2013).
However, other parameters with additional functions were applied to find a structural
refinement with better quality and reliability. These parameters, such as the scale factor, 2θ offsets,
sample position, and the background coefficient number from twelve to twenty-four, played a crucial
role in achieving the best convergence (Carruthers e Watkin, 1979; McCusker et al., 1999). They were
used to introduce more background terms with the Chebyshev-1 polynomial coefficients (McCusker et
al., 1999), size (nm), isotropic microstrain, refinement controls with an Analytic Hessian as input at
five maximum cycles to pristine BaWO 4 crystals and analytic Jacobian (Toby e Von Dreele, 2013) for
modified BaWO4 microcrystals/x.AgNPs with (x = 1, 2, and 4% at mass) to identify singularities and
remove them from the least-squares function from refinement, instrument parameters, samples
parameters, adjusting the diffraction peaks shape with Thompson-Cox-Hastings, and Finger-Cox-
Jephcoat functions (Thompson et al., 1987; Finger et al., 1994), March-Dollase model (March, 1932;
Dollase, 1986; Zolotoyabko, 2009), spherical harmonic coefficients to for eighteen (Sitepu, 2002;
Beyer et al., 2020), lattice parameters (a, b, and c), three angles (α, β, and γ), unit cell volume, atomic
positions (x, y, and z), and Uisotropic factor.
Figs. SM1(a–d) displays the Rietveld refinement plot of pristine BaWO 4 microcrystals and
modified BaWO4 microcrystals/x.AgNPs with (x = 1, 2, and 4% at mass) prepared by IIHSFC method
at 90 ºC for 30 seconds and photoreduction method after 15 min, respectively.

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Figs. SM1(a–d): Rietveld refinement plot of (a) pristine BaWO4 microcrystals, and modified BaWO4 microcrystals/xAgNPs
with (b) x = 1%, (c) x = 2%, (d) x = 4% at mass, respectively

In Figs. SM1(a–d), it can be seen that the structural refinement using the Rietveld refinement

method confirmed that both the single BaWO 4 crystals and the modified BaWO 4 microcrystals with

xAgNPs (x = 1, 2, and 4% at mass) have a scheelite-type tetragonal structure. This structure exists at

room pressure and temperature, with space group (I41/a), point group symmetry (C 64 h), and four

molecular formula units per unit cell (Z = 4) (Kaur et al., 2020). Slight differences in intensity scale

were noticed between the experimental and calculated XRD patterns, as indicated by the line (YObs line

v
– YCalc line) in the Rietveld refinement plots in Figs. SM1(a–d). The obtained experimental data using

Rietveld refinement for the four samples can be found in Tables SM1(a–d).

Table SM1: Rietveld refinement data for (a) pristine BaWO4 microcrystals, and modified BaWO4 microcrystals/xAgNPs

with (b) x = 1%, (c) x = 2%, (d) x = 4% at mass, prepared by injection fast method at 90 °C for 30 seconds and

photoreduction method after 15 min, respectively

(a) Atoms Wyckoff positons Site x y z Uiso

Ba 4b -4.. 0.0 0.25 0.625 0.00967

W 4a -4.. 0.0 0.25 0.125 0.00744

O 16f 1 0.25381 0.13871 0.0462 0.02547

a = 5.61602(5) Å; b = 5.61602(5) Å; c = 12.72508(14) Å; c/a = 2.2659;  = 90.0º;  = 90.0º;  = 90.0º; Volume =
401.345(7) Å3; Z = 4;  = 6.3746 g/cm³; Rexp = 7.452%; RBragg = 7.610%; Rwp = 10.964%; χ² = 1.471, and S = 1.212.
(b) Atoms Wyckoff positons Site x y z Uiso

Ba 4b -4.. 0.0 0.25 0.625 0.00843

W 4a -4.. 0.0 0.25 0.125 0.00352

O 16f 1 0.2543 0.13383 0.05542 0.03245

a = 5.61838(4) Å; b = 5.61838(4) Å; c = 12.73173(21) Å; c/a = 2,26608;  = 90.0º;  = 90.0º;  = 90.0º; Volume =
401.893(6) Å3; Z = 4;  = 6.3659 g/cm³; Rexp = 7.437%; RBragg = 8.18%; Rwp = 11.87%; χ² = 1.596, and S = 1.263.
(c) Atoms Wyckoff positons Site x y z Uiso

Ba 4b -4.. 0.0 0.25 0.625 0.00135

W 4a -4.. 0.0 0.25 0.125 0.02692

O 16f 1 0.2352 0.1403 0.0516 0.03683

a = 5.616617(7) Å; b = 5.616617(7) Å; c = 12.72857(25) Å; c/a = 2.26623;  = 90.0º;  = 90.0º;  = 90.0º; Volume =
401.540(8) Å3; Z = 4;  = 6.3715 g/cm³; Rexp = 7.741%; RBragg = 7.221%; Rwp = 9.970%; χ² = 1.288, and S = 1.135.
(d) Atoms Wyckoff positons Site x y z Uiso

Ba 4b -4.. 0.0 0.25 0.625 0.01052

W 4a -4.. 0.0 0.25 0.125 0.01361

O 16f 1 0.25631 0.15821 0.05182 0.02235

a = 5.619335(31) Å; b = 5.619335(31) Å; c = 12.73611(27) Å; c/a = 2.2664;  = 90.0º;  = 90.0º;  = 90.0º; Volume =
402.167(11) Å3; Z = 4;  = 6.3615 g/cm³; Rexp = 7.800%; RBragg = 7.824%; Rwp = 10.366%; χ² = 1.329, and S = 1.152.

Based on Rietveld refinement calculations and the data in Tables SM1(a–d), our original

BaWO4 crystals and modified BaWO4 microcrystals/xAgNPs with (x = 1, 2, and 4% at mass) created

vi
using the injection method at 90 °C for 30 seconds demonstrated excellent results meeting the

crystallographic criteria. There were minor variations in the (x, y, z) atomic positions for oxygen (O)

atoms, while the barium (Ba) and tungsten (W) atoms held specific (x, y, z) atomic positions within

the tetragonal lattice, remaining consistent throughout the structural refinement process. Our Rietveld

refinement results, as indicated by the R-values, consistently matched the crystallographic patterns

found in the ICSD card No. 193493 (Shivakumara et al., 2015). In this context, the oxygen atoms

promote distortions in both the O–W–O and O–Ba–O bonds, leading to distorted tetrahedral [WO 4]

clusters and distorted deltahedral [BaO8] clusters, as illustrated in Figs. SM2(a–d).

Clusters coordination and electron density maps analysis

The Figs. SM2(a–d) illustrate the unit cells with scheelite-type tetragonal structure of pristine

BaWO4 microcrystals and their modification with x%AgNPs (where x = 1, 2, and 4%). The unit cell

for Ag-metallic with cubic structure is also shown in Fig. SM2(e) for comparison.

vii
 (e)

Figs. SM2(a–d): Schematic representation of units cells with tetragonal lattice for (a) pristine BaWO4 microcrystals and

modified BaWO4 microcrystals/xAgNPs with (b) x = 1, (c) x = 2, (d) x = 4% at mass with distorted tetrahedron [WO4]

clusters at diferente values of (O–W–O) bonds angles, deltahedron [BaO 8] clusters, and (e) unit cell for Ag-metallic with

face-centered cubic lattice and exclusive presence of cuboctahedron [AgAg 12] clusters, respectively.

The unit cells with tetragonal structure for pristine BaWO 4 microcrystals and modified BaWO4

microcrystals/xAgNPs with different AgNPs (x = 1, 2, and 4% mass) were modeled using

Visualization for Electronic and Structural Analysis (VESTA) software (version 3.5.8 for Windows

11, 64 bits) (Momma e Izumi, 2008; Momma e Izumi, 2011). This was done using the lattice

parameters and atomic positions obtained from the Rietveld refinement data listed in Tables SM1(a–

d). Figs. SM2(a–d) illustrate the lattice modifiers assigned to barium (Ba) atoms, forming distorted

viii
deltahedron [BaO8] clusters with symmetry (D2d), which are polyhedrons with a snub disphenoid

shape; a Johnson solid, also known as the siamese dodecahedron with 8 vertices, 12 faces, and 18

edges. Moreover, the lattice former related to tungsten (W) atoms presents distorted tetrahedron

[WO4] clusters with symmetry (Td), which are polyhedrons with 4 vertices, 4 faces, and 4 edges. In

this case, the oxygen atoms are able to induce distortions on both the O–Ba–O or O–W–O bonds

within the lattice. Furthermore, the AgNPs only exhibit a type of coordination cluster that is attributed

to a cuboctahedron [AgAg12] clusters with radial equilateral symmetry. This cluster has 8 triangular

faces and 6 square faces, forming an Archimedean solid with 12 vertices, 14 faces, and 24 edges (as

shown in Fig. SM2(e)). However, it is challenging to draw any conclusions about the existence of

AgNPs from the XRD measurements (Wang et al., 2009). Therefore, we referenced the literature for

the indexation of Ag-metallic with a cubic structure using the respective ICSD card No. 604630 (Jette

e Foote, 1935). Consequently, we have included the Raman spectroscopy data in the next section.

Figs. SM3(a–h) show the 2D electron density isolines inside the (1×1×1) unit cell on the (100)

and (001) planes for pristine BaWO4 microcrystals and BaWO4 microcrystals modified with x%

AgNPs (x = 1, 2, and 4% at mass), respectively.

ix
 5

x
Figs. SM3(a–h): Electron density maps in the (100) and (001) planes of (a,e) pristine BaWO4 microcrystals, and modified
BaWO4 microcrystals/x.AgNPs with (b,f) x = 1%, (c,g) x = 2%, and (d,h) x = 4% at mass, respectively.
The 2D isolines of electron density models were calculated using the Fourier transform

structure factor from the structure parameters, such as lattice parameters (a, b, and c), angles (α, β, and

γ), unit cell volume, atomic positions (x, y, and z), and Uisotropic factor, and atomic scattering factors of

free atoms obtained from the Rietveld refinement data for pristine BaWO4 microcrystals, modified

BaWO4 microcrystals/xAgNPs with (x = 1, 2, and 4%), as shown in Figs. SM3(a–h), respectively.

These refined structural data were employed in the VESTA software (version 3.5.8 for Windows 11®-

64 bits) (Momma e Izumi, 2008; Momma e Izumi, 2011) to build the 2D isolines electron density

models using a high resolution from 0.012 to 0.015 Å. These figures display different and sensible

color scales on each specific crystallographic plane, indicating zones with high and low electron

densities. As shown in Fig. SM3(a), the red color areas exhibit a high electronic density in the (100)

plane; yellow and green color regions are ascribed to the medium electron densities, while the cyan and

blue color regions are related to the low and absence of electronic charge. It is possible to note the

presence of non-homogeneous electronic charge distributions near the O–W–O bonds related to an

atomic displacement, indicating the existence of different degrees of distortions on the tetrahedral

[WO4] clusters, as shown in Figs. SM3(a–d). Moreover, in Figs. SM3(a–d), we have observed two W

atoms, two Ba atoms, and six O atoms on the (100) plane, but in Figs. SM3(c), it is possible to note a

high electron density due to specific distortions to modified BaWO 4 microcrystals/2%AgNPs, as shown

in Fig. SM3(c). Finally, the 2D isolines of the electron density maps on the (001) crystallographic

plane are illustrated in Figs. SM3(e–h) for pristine BaWO4 microcrystals, modified BaWO4

microcrystals/xAgNPs with (x = 1, 2, and 4%), where it is possible to note the presence of four O

atoms, where W and Ba atoms are bonded to these same O atoms. Therefore, in Fig. SM3(g), this

modified BaWO4 microcrystals/2%AgNPs prepared by IIHSFC method at 90 ºC for 30 seconds and

xi
photoreduction strategy after 15 min present a specific degree of partial orientation at [001] direction,

which exhibits a minor electronic charge density on the (100) plane due to smaller areas in red color.

These results corroborate the cluster's coordination model illustrated earlier in Fig. SM2(c).

Fourier transform infrared (FTIR) spectroscopy analysis

Fig. SM4(a–d) illustrates the FT-IR spectra of pristine BaWO 4 microcrystals and modified

BaWO4 microcrystals/xAgNPs with (x = 1, 2, and 4% at mass) were prepared using the injection

method at 90 °C for 2 min and the photoreduction method after 15 min, respectively.

Figs. SM4(a–d): FT-IR spectra of (a) pristine BaWO4 microcrystals, and modified BaWO4 microcrystals/xAgNPs with (b) x
= 1, (c) x = 2, (d) x = 4% at mass, respectively. The dashed vertical (---) lines indicate the positions of the active modes in
the infrared.
According to the general equation (I) and the literature (Shi e Fu, 2021), the tungstates with a

scheelite-type tetragonal structure exhibit only eight stretching and/or bending active IR vibrational

modes in FT-IR spectra, as represented by equation (I):

Γ(Infrared)} = 5Au + 3Bu + 5Eu (I)

Our research successfully identified three fundamental infrared-active vibrational modes in the

IR spectra related to Au, Bu, and Eu modes. Although we weren't able to detect other active IR modes

xii
due to equipment limitations, the FT-IR spectrophotometer (see Fig. SM4(a–d)) revealed two robust

absorption bands associated to Eu and Au modes at approximately 802 and 870 cm -1 found in pristine

BaWO4 crystal and modified BaWO4 microcrystals with x% AgNPs (where x = 1, 2, and 4% at mass).

These significant vibrational modes are directly linked to the asymmetric stretching of the O–W–O

bonds within the tetrahedral [WO4] clusters (Karthik et al., 2021; Priya et al., 2013; Ramezanalizadeh

et al., 2018). In addition, one absorption band can also be observed at approximately 453 cm -1 related to

the dispersion of Ag–Ag bonds from  AgNPs, confirming the surface modification of BaWO 4

microcrystals. However, it was impossible to observe a shift in the absorption bands of the decorated

materials about the pristine BaWO4 microcrystals, indicating that there was only a surface modification

with the addition of AgNPs (Habtamu et al., 2021; Gowri et al., 2023; Carvalho et al., 2020).

SEM image, EDXS spectra, and EDXS mapping of pristine BaWO4 crystals and modified BaWO4
microcrystals/x%AgNPs (x = 1%, 2% and 4% at mass).

Figs. SM5(a): SEM image with measured at least several points on the pristine BaWO4 microcrystals
deposited onto carbon tape, EDXS mapping image, and EDXS spectrum, respectively.

xiii
Figs. SM5(b): SEM image with measured at least several points on the modified BaWO 4
microcrystals/1%AgNPs deposited onto carbon tape, EDXS mapping image, and EDXS spectrum,
respectively.

Figs. SM5(c): SEM image with measured at least several points on the modified BaWO 4
microcrystals/2%AgNPs deposited onto carbon tape, EDXS mapping image, and EDXS spectrum,
respectively.

xiv
Figs. SM5(d): SEM image with measured at least several points on the modified BaWO 4
microcrystals/4%AgNPs deposited onto carbon tape, EDXS mapping image, and EDXS spectrum,
respectively.

Table SM2: Data obtained to absolute rate constant (k), photodegradation rate (PDR), coefficient of
correlation (R2), and standard deviation (SD) after PC assays of TC antibiotic.

Catalysts k{ } PDR R² SD SBET Literature

Method
Synthesis (min) (%) (%) ( ) (m²/g)

UAHT ZnWO4 0.0105 74 – – 37 Huerta-Flores et al.

7 2018
HT Cu2WS4/Bi2WO6 0.0051 80 – – 27.92 Huo et al.
9 2023
SC Sb2WO6-30 0.0021 55 – – – Jeyaprakash et al.
2023
SSR BaMoO4 – 85 – – – Jin et al.
2024
OPC 20%Ag2MoO4/8%SrWO4/g-C3N4 0.0380 90.62 – – 73.72 Peng et al.
2024
IIHAS Photolysis 0.0006 21.1 0.95587 0.00003 – 
033 6
IIHAS BaWO4 0.0035 74.1 0.95305 0.00022 3.03 
9 1
IIHAS BaWO4/1%AgNPs 0.0033 67.3 0.88654 0.00033 2.75 
3 1
IIHAS BaWO4/2%AgNPs 0.0049 90.0 0.90349 0.00045 5.79 
8 2
IIHAS BaWO4/4%AgNPs 0.0019 57.2 0.85458 0.00022 2.08 
6 4

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UAHT = Ultrasound-Assisted Hydrothermal; UT = Hydrothermal; SSR = Solid State Reaction; OPC = One-Pot Calcination; IIHAS = I njection of Ions
Into a Hot Aqueous Solution; Linear fit for all the curves, and  = This Work.

Fig. SM6: FT-IR spectra of modified BaWO4 microcrystals/x.AgNPs with x = 2% at mass at 0th cycle (before photocatalytic
assays) and modified BaWO4 microcrystals/x.AgNPs with x = 2% at mass at fourth cycle (after photocatalytic assays),
respectively. The dashed vertical (---) lines indicate the positions of the active modes in the infrared.

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