Understanding the Chemical Mechanism behind Photoinduced Enhanced Raman Spectroscopy

Photoinduced enhanced Raman spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with a 680% Raman signal enhancement of adsorbed analytes over that of SERS. Despite the explosion in recent demonstrations, the PIERS mechanism remains undetermined. Using X-ray and time-resolved optical spectroscopies, electron microscopy, cyclic voltammetry, and density functional theory simulations, we elucidate the atomic-scale mechanism behind PIERS. Stable PIERS substrates were fabricated using self-organized arrays of TiO2 nanotubes with controlled oxygen vacancy doping and size-controlled silver nanoparticles. The key source of PIERS vs SERS enhancement is an increase in the Raman polarizability of the adsorbed analyte upon photoinduced charge transfer. A balance between improved crystallinity, which enhances charge transfer due to higher electron mobility but decreases light absorption, and increased oxygen vacancy defect concentration, which increases light absorption, is critical. This work enables the rational design of PIERS substrates for sensing.

2) I'm not sure if it's a typo or not, but I don't understand the reference to 1518 on p8 l46 left column. If I look at Figure 5 the band that appears to increase in the charge transfer amine complex is around 1600, but the vibrational mode plotted at the top is 1518.
3) Given the variability in SERS enhancements, sometimes even within a spectra, it is difficult to believe that the relative line intensities in Red and Blue in Figure 5a should be interpreted as clear evidence of charge transfer. (For example, the wavelength dependent enhancement factors of the substrate could simply change by a little bit in this range and it would lead to the -not large -differences in band intensities relative to the massive (10^6) PIERS/SERS enhancements. 4) Given that the authors rely on electrochemical measurements for some of their study, it seems that measuring changes in the spectra under an applied potential could significantly strengthen their claims. 5) pH plays a large role in binding geometry and SERS spectra for compounds such as RhB. The authors should comment on this in their manuscript and state what, if anything, they did to control for it. For example, experiments could be done in the presence of buffered solutions of different pH to further test their hypotheses. Figure S6 -Caption is missing descriptions for panels (b) and (c) 6) Figure S13 -Caption is missing description for panel (d) 7) Figure S17 -I believe the x-axis label is incorrect on (d)

5)
Overall, the amount of work here is impressive, but the system is very complicated making a clear attribution of the mechanism difficult.

Reviewer: 2
Comments to the Author This manuscript reinvestigates the origin of photo-induced enhanced Raman scattering (PIERS), suggesting that, contrary to the hypotheses proposed so far, at the basis of this effect there is a significant increase of Raman polarizability caused by photonic excitation.
These results offer a new interpretation of PIERS. Previous literature associated the effect to the increase of electron density nearby the noble metal nanoparticles, which is assisted by titanium vacancy subband gap energy levels introduced upon UV irradiation. Going more into details, the main steps of PIERS generation are actually the same as proposed in previous literature, i.e.: (i) absorption of visible light by Ti vacancy defect states; (ii) electron transfer from defect states to the conduction band of TiO2, (iii) electron transfer to the Fermi level of plasmonic nanoparticle and (iv) electron transfer from plasmonic nanoparticle to the adsorbed analyte. According to DFT calculations reported in this work, it would be the latter step that determines the increase of molecular polarizability and, eventually, the enhanced Raman response.
Thus, this study suggests that PIERS is mainly due to a chemical, not to a merely electromagnetic enhancement, and this chemical enhancement is not caused by metal-to-ligand type charge transfer, but it is due to the bond between metal nanoparticles (fed by electrons from TiO2 upon irradiation) and the analyte.
This conclusion is interesting, however, to make it more convincing, I would suggest addressing the following points: 1) The authors compared defective TiO2, i.e. annealed in argon at high temperature, with as prepared, amorphous titania. It would be more informative to compare the PIERS substrate (based on defective TiO2) with another TiO2 substrate annealed in air at the same temperature (400°). In this way the effect of titania oxygen vacancies would be clearly elicited.
2) Related to the previous point, at Page 4, the statement "a controlled amount of oxygen defects…" suggests that there is a full control of oxygen defects and their density. However, in the remaining part of the manuscript there are neither direct evidence of this control nor any quantification of defect density. XPS data only give the status of the sample, but the key point is to develop a protocol to precisely control the amount of Ti3+ in PIERS substrates. This is mandatory, in view of developing a tool that is relevant for sensing and chemical analysis. I would suggest to better clarify this point, as the oxygen defect states are the cornerstone of the whole PIERS effect.
3) Raman experiments should be run very carefully, in order to achieve reliable data. In particular, data should be acquired avoiding probing regions with local accumulations of the analyte and a statistically relevant number of regions should be analyzed, with an indication of relative standard deviation. A precise description of data acquisition and analysis is missing and should be added. 4) Supporting Information. Figure S2 shows that the Raman detection of RhB is strongly dependent on sputtering time, which means that there is a dependence on the density of distribution of silver clusters. Is this experimental observation coherent with the mechanism proposed? In other words, is polarizability affected by the nanoparticle size? This aspect is not clear, as nanoparticle size seems to provide a greater contribution to Raman enhancement. Please check some typos, for example page 7, row 29, right column: "florescence" Author's Response to Peer Review Comments:

Response to reviewers
We thank the editor and reviewers for their insightful comments and the opportunity to improve the manuscript. We greatly appreciate the feedback from all reviewers who emphasise that the manuscript employs "an impressive array of different experimental techniques to elucidate the mechanism" and that we propose a mechanism of photo-induced enhanced Raman spectroscopy (PIERS) "contrary to the hypotheses proposed so far" with an "interesting and thought-provoking claim in the conclusion" and conclude that the "amount of work here is impressive".
The mechanism of PIERS is multi-faceted, which we highlight in our introduction and as pointed out by the reviewers. While previous works have proposed various hypotheses 1 , they lack detailed timeresolved spectroscopic, structural, and electrochemical evidence supporting it. Using a wide range of tools, we have performed the first mechanistic determination of the energy levels and kinetics relevant in PIERS for a model molecule: Rhodamine B. We have contributed a key new piece of the puzzle in terms of dynamic polarizability changes due to charge transfer that must be considered. Additionally, we apply structural tools such as high-resolution TEM and XRD to determine the role of crystallinity and defect density on the charge transfer steps necessary for PIERS enhancement, for the first time. We believe this understanding is generalizable to other molecular systems, and now provide new experiments: • Raman spectra for a molecule whose energy level alignment is unfavourable for PIERS, yet acts as a standard Raman probe -1-octanethiol 2 , • PIERS spectra testing the effect of annealing temperatures, • PIERS spectra in different annealing environments (air v.s. Ar) to clarify the role of oxygen vacancies.
Our work not only tests a hypothesis for the final step of the PIERS enhancement, but also excludes three other hypotheses (charge transfer resonance Raman, increased plasmonic enhancement, and fluorescence quenching). We believe this is a significant contribution to determining the mechanism of the PIERS process.
We have highlighted all changes in the main manuscript and supplementary information in red.

Reviewer #1:
"The major technical advance claimed here is elucidation of the mechanism underlying phot-induced enhanced Raman spectroscopy (PIERS). Specifically, the authors claim that excitation of oxygen vacancy sites leads to a cascade of processes ending with charge transfer to the adsorbed dye (RhB) molecule. The authors employ an impressive array of different experimental techniques to elucidate the mechanism but given the complexity of the system under study most of the evidence presented falls into the "circumstantial" category. There is no doubt that a significant Raman enhancement is observed by creating nanoparticle substrates on defect containing crystalline TiO2. However, the final conclusion of a charge transfer process is complicated by several factors: lack of independent verification of the RhB surface adsorption geometry and the diffuse appearance of the RhB spectra." We thank the reviewer for highlighting the array of experimental techniques used, however we disagree that the evidence is circumstantial. We provide, for the first time, direct evidence of the kinetics of the previously conjectured photo-induced charge transfer of an excited electron from the defect states of TiO2 to Ag using static spectroscopy and time-resolved nanosecond photoluminescence spectroscopy. Furthermore, we showed using X-ray photoelectron spectroscopy (XPS) the shift in binding energies of Ag and Ti that indicates static interfacial charge transfer.
In the final step of charge transfer enhancing the Raman polarizability of RhB, our conclusion relies on a comparison of the energy levels measured independently through cyclic voltammetry to show that such a charge transfer is energetically favourable, and also through a comparison of the Raman spectra to DFT calculations. The DFT calculations of Ag adsorption energy at several sites and an application of the Moskovitz selection rules for enhanced Raman 3 , as mentioned in the main text, allow us to assign the predominant orientations of RhB on the surface. Indeed, there is likely a mixture of orientations. The Raman measurement technique is only sensitive to some of these orientations, due to the different Raman polarizabilities of different binding geometries, and SERS/PIERS preferentially providing signals from the ones with the highest polarizabilities. In all cases calculated, the coordination of RhB to Ag increases the Raman polarizability, except for coordination of RhB's xanthene moiety to Ag; this observation further supports our conclusion that the interaction of Ag with RhB occurs via the nitrogen atom.
We modify the main text below to highlight this: "The most likely binding geometry was determined by calculating the Raman modes of RhB+ using DFT in Fig. 5(a) (B3PW91/6-31G+(d,p) and LANL2DZ(for Ag)), and applying Moscovitz's SERS surface selection rules 64 : normal modes with a large polarizability component normal to the metal's surface will be enhanced. In Fig. 5(a), both the PIERS and SERS substrates show an enhanced Raman intensity of the antisymmetric xanthene ring stretch at ~1370 cm -1 (theory: 1344 cm -1 ) and symmetric amine stretches at ~1200 cm -1 (theory: 1260cm -1 ) relative to the pure xanthene ring stretch at 1646 cm -1 . As the enhanced xanthene ring stretches have their displacement vectors aligned along the long axis of the RhB molecule ( Fig. 5(c)), this implies that the binding needs to occur via a functional group face that is aligned to RhB's long axis. This leaves only one option: the nitrogen fragment of the RhB must bind strongly to the Ag surface. This conclusion is supported by the increased intensity of peaks associated with a xanthene ring carbon-nitrogen stretch (1380-1390 cm -1 ). If RhB were lying fully flat, it would be the out-of-plane modes that would be enhanced, at the expense of the in-plane modeswhich is not observed. Marchi et. al. 59 also found that RhB prefers to coordinate to Ag via its amine groups. As the amine's motion is hindered, the fluorescence quantum yield should increase as the greater rigidity reduces the rate of internal conversion -which we observe as an overall increase in the Raman background ( Figure S3). However, the absolute determination of the range of likely binding geometries is challenging, and dependent on nuances such as local pH. Despite that, all simulations with Ag present increase the Raman polarizability of RhB, except for coordination to the xanthene, which further supports the coordination of Ag to N dominating the SERS and PIERS spectra." The surface selection rules allow us to assign the predominant orientation of RhB on the surface. However, we agree that there are further steps to determining the absolute orientation and indeed the range of orientations that RhB must have on the surface of Ag and have updated the text below to reflect this. Further ultrafast spectroscopic techniques such as polarized surface-enhanced sumfrequency generation spectroscopy 4 and surface-enhanced hyper-Raman spectroscopy 5 may determine the orientation, however such experiments are outside of the scope of this letter. We emphasize that we are not explicitly determining all the possible geometries of RhB binding on an Ag surface, and only highlight the few likely to be relevant to the PIERS enhancement process.
"An interesting and thought-provoking claim in the conclusion is: now that we understand the mechanism we can rationally design systems to use the PIERS mechanism. This claim would be more convincing if the authors demonstrated this with another molecule.
As an aside, no rationale is given for choosing RhB We thank the reviewer for recognizing our interesting conclusions. While more has been done to determine the binding of Rhodamine-6-G (R6G), at the laser wavelength used to excite the PIERS process (488 nm), R6G possess strong absorption bands (Fig. R1) unlike RhB. This will give rise to a large fluorescence background and resonance Raman enhancement which would complicate disentangling the true contribution of the PIERS mechanism. Hence, we do not perform experiments with R6G. This is a key contribution of our work, as previous PIERS works 7-15 use dye molecules with strong resonance Raman enhancement exactly at the laser excitation wavelength. We highlight this further in the introduction: "Prior works have proposed a charge-transfer based enhancement for many dye molecules in pure/defect engineered semiconductors [14][15][16][17][18][19][20][21] , semiconductor heterostructures 22,23 or semiconductormetal heterostructures 24 . However, such works have used conditions in which the dye molecule (such as Rhodamine-6-G) is on-or near-resonance with the excitation laser 14,16,19,23,[25][26][27][28][29] , thus having resonance Raman enhancements in addition to substrate-induced enhancements, or claim charge transfer without providing evidence for the exact mechanism 17,18,30 . Indeed only a few studies 14,20,24,27,31,32 show evidence that bona-fide charge transfer resonances between localized molecular states to semiconductor bands are boosting the observed Raman signals, while others 33, 34 suggest this but do not provide any direct evidence of energetically favorable band alignments. No effort has been made yet to map out the energy levels involved to establish the mechanism for Raman signal enhancement by PIERS." Future work will measure multiple molecules. However, for this work, the full range of analytical techniques used (cyclic voltammetry, nanosecond time resolved spectroscopy, x-ray photoelectron spectroscopy, etc.) have only been performed on one model molecule (RhB).
We have performed a new experiment using 1-octanethiol which we share below. This system displays little to no PIERS enhancement (main peak at 1595 cm -1 is only 20% higher, attributed to sample variation) due to misaligned energy levels for charge transfer with a deep HOMO level of -3.5 eV 16 from a metal's Fermi level and a HOMO-LUMO gap of 8-9 eV 17 .This new data further supports our proposed mechanism for PIERS. We now include this as a discussion in the main text page 7, and in SI Section S9. We thank the reviewers and make changes to streamline references to the SI in the main text. We emphasize that our extensive SI is to provides additional information/control studies for our mechanism. All critical information is contained in the main figures.

2) I'm not sure if it's a typo or not, but I don't understand the reference to 1518 on p8 l46 left column.
If I look at Figure 5 the band that appears to increase in the charge transfer amine complex is around 1600, but the vibrational mode plotted at the top is 1518.
We thank the reviewer for pointing this out and have corrected this in the manuscript. Indeed, it was a typo; the mode of interest is at 1580 cm -1 .

3) Given the variability in SERS enhancements, sometimes even within a spectra, it is difficult to believe that the relative line intensities in Red and Blue in Figure 5a should be interpreted as clear evidence of charge transfer. (For example, the wavelength dependent enhancement factors of the substrate could simply change by a little bit in this range and it would lead to the -not large -differences in band intensities relative to the massive (10^6) PIERS/SERS enhancements.
We show consistent replicate SERS measurements across the sample, showing similar relative intensity changes in Supplementary Section S1, with consistent enhancement of peaks at 1580 cm -1 in the PIERS relative to the SERS substrate. We also highlight our measurement protocol in response to Reviewer #2's third question below, and show data at different concentrations of RhB sampled in different locations.
While we agree that SERS measurements can be variable on certain substrates and single nanostructures, in these measurements, we took care to measure with a low numerical aperture objective lens, averaging spectra over an area several microns across in multiple measurements. Furthermore, the conclusion of static charge transfer leading to an increased Raman polarizability is supported through cyclic voltammetry measurements.
Our work not only offers a good hypothesis for the final step of the PIERS enhancement, but also examines and excludes three other hypotheses (charge transfer resonance Raman, increased plasmonic enhancement, and fluorescence quenching). Other explanations are possible, but we propose the one most consistent with available evidence.

4) Given that the authors rely on electrochemical measurements for some of their study, it seems that measuring changes in the spectra under an applied potential could significantly strengthen their claims.
We use the electrochemical measurement to determine the HOMO and LUMO levels of RhB on the PIERS substrate surface. For the PIERS mechanism however, all charge transfer is photo-induced by laser excitation, hence an applied external potential would not reproduce the same effect due to a lack of plasmonic optical field localization driving external charge transfer 18, 19 through e.g. hot electrons. However, this could be useful for tuning the molecule's HOMO and LUMO levels statically, which is an excellent suggestion. Efforts to build a custom microscope-compatible spectroelectrochemical cell are underway, however it is outside the scope of this work.

5) pH plays a large role in binding geometry and SERS spectra for compounds such as RhB. The authors should comment on this in their manuscript and state what, if anything, they did to control for it. For example, experiments could be done in the presence of buffered solutions of different pH to further test their hypotheses.
All samples are dry during measurement and RhB was deposited on the surface from an ethanol solvent and subsequently dried. Indeed, there are changes in the protonation state of RhB upon binding to the surface, which is hard to control on the PIERS substrate. Since samples are dry in most experiments of PIERS thus far 1, 20 , control of pH using a buffer is difficult. We now discuss these nuances in the main text: "The absolute determination of binding geometry is challenging, and dependent on nuances such as local pH." Figure S6 -Caption is missing descriptions for panels (b) and (c) 7) Figure S13 -Caption is missing description for panel (d)

8) Figure S17 -I believe the x-axis label is incorrect on (d)
We are grateful to the reviewer for noticing these and have implemented these corrections.

Thus, this study suggests that PIERS is mainly due to a chemical, not to a merely electromagnetic enhancement, and this chemical enhancement is not caused by metal-to-ligand type charge transfer, but it is due to the bond between metal nanoparticles (fed by electrons from TiO2 upon irradiation) and the analyte.
We thank the reviewer for their positive comments and highlight that while the initial steps are consistent with that proposed in the wider literature, we now show actual spectroscopic and timeresolved nanosecond kinetic evidence of the PIERS process, which was not measured before.

1)
The authors compared defective TiO2, i.e. annealed in argon at high temperature, with as prepared, amorphous titania. It would be more informative to compare the PIERS substrate (based on defective TiO2) with another TiO2 substrate annealed in air at the same temperature (400°). In this way the effect of titania oxygen vacancies would be clearly elicited.
In response to this reviewer's helpful observation, we report new experimental results showing the effect of the different annealing temperatures and environments within the SI (section S8). In the main text, we highlight the role of defects, which increase visible laser absorption at the cost of reduced charge transfer mobilities. A balance between crystallinity and defect concentration is needed. We now also find an optimum annealing temperature in Ar atmosphere of 600°C (Fig. R3b) for PIERS enhancement. At this optimum temperature, annealing in an oxygen-deficient Ar atmosphere v.s. air (Fig. R3c) is critical for higher PIERS enhancements. We now include an additional discussion in the SI Section S8: "By changing the annealing temperature with constant annealing treatment time (1 hr), we vary the amount of anatase v.s. rutile within the sample and the overall crystallinity 21 . This impacts the charge transfer process in PIERS upon photoexcitation, with greater crystallinity often improving charge transfer, showing an optimum at 600°C with a mixture of rutile to anatase. Past that, the PIERS enhancement decreases, due to changes in the charge transfer mechanism, which could be due to increasing concentration of the rutile phase which has a reduced charge diffusion length relative to anatase 22 , and also a decreased absorption of light as defect density is reduced."

2)
Related to the previous point, at Page 4, the statement "a controlled amount of oxygen defects…" suggests that there is a full control of oxygen defects and their density. However, in the remaining part of the manuscript there are neither direct evidence of this control nor any quantification of defect density. XPS data only give the status of the sample, but the key point is to develop a protocol to precisely control the amount of Ti3+ in PIERS substrates. This is mandatory, in view of developing a tool that is relevant for sensing and chemical analysis. I would suggest to better clarify this point, as the oxygen defect states are the cornerstone of the whole PIERS effect.
We now estimate the defect density from XPS measurements as 17 x10 3 µm -2 (details now included in SI section S3) and included a discussion in the text citing our previous work 21, 23 on controlling defect density in TiO2 and crystallinity, along with the new work showing that annealing temperature controls the PIERS enhancement magnitude, with an optimum in annealing temperature. We emphasize further the role of balance between the increased crystallinity required for efficient charge transfer, and increased defect density which improves light absorption yet reduces charge transfer efficiency. This was also investigated by Glass et. al. 20 , and we emphasize that finding exact defect densities of Ti 3+ is non-trivial, as it requires positron annihilation lifetime spectroscopy 24 which is not a readily available lab-based technique and is a bulk measurement often requiring a large quantity of material. In the main text page 4, we now add: "Changing the crystallinity through different annealing temperatures also reveals an optimum in PIERS enhancement, due to increasing rutile fraction with lower charge mobility and decreased defectassisted light absorption, further supporting this hypothesis (SI Section S8)."

3)
Raman experiments should be run very carefully, in order to achieve reliable data. In particular, data should be acquired avoiding probing regions with local accumulations of the analyte and a statistically relevant number of regions should be analyzed, with an indication of relative standard deviation. A precise description of data acquisition and analysis is missing and should be added.
We thank the reviewer for highlighting the importance of sampling in Raman spectroscopy experiments, which we have taken into consideration by performing replicate experiments across our samples and have now included further details in the methods section as below: "Raman spectra were acquired using a Renishaw RM1000 Raman Microprobe comprising a single grating spectrograph of 2400 g/mm with a holographic notch filter removing Rayleigh scattered light below 150 cm -1 , with a 20 × objective lens (N.A. 0.5) providing a spot size at the surface of 1 -2 µm and entrance slit width of 50 µm. Excitation at 488 nm was provided by an air-cooled Spectra-Physics Argon ion laser at 1 mW. The test molecule used in this study was Rhodamine B (RhB). The acquisition time was 60 sec per spectrum with 3 accumulations. For tests on the PIERS and SERS substrates, ~5 μL of RhB solution (10 -5 molL -1 , 10 -6 molL -1 , and 10 -7 molL -1 ) was deposited onto each substrate and dried in the air for 5 min prior to Raman spectra acquisition. All spectra presented are collected over at least 3 locations and averaged."

4)
Supporting Information. Figure S2 shows that the Raman detection of RhB is strongly dependent on sputtering time, which means that there is a dependence on the density of distribution of silver clusters. Is this experimental observation coherent with the mechanism proposed? In other words, is polarizability affected by the nanoparticle size? This aspect is not clear, as nanoparticle size seems to provide a greater contribution to Raman enhancement.
Plasmonic optical field enhancement and hence SERS are indeed strongly controlled by nanoparticle size. However, the PIERS enhancement vs. SERS is robust for the same Ag nanoparticle size distributions. Using thermal dewetting, we can control the size distribution of Ag nanoparticles, which we show in SI Fig. S6, and we show spectra and enhancement factors of PIERS and SERS structures with different Ag sputtering times in Table S2. We see that the increase of PIERS signals relative to SERS is consistent across multiple samples with different size distributions.

5)
Page 8: "The PIERS substrate showed a 580% enhancement of Raman signals than the equivalent SERS substrate without defective crystalline TiO2". How do you calculate it?
We calculated the PIERS enhancement in SI Section S1, and now expand further with a more robust estimation of peak areas instead of intensities as before, and obtain more accurate enhancement factors: The Raman enhancement factor (EF) is calculated using Eqn (S1) below, via integrating the area of the peak beneath two different Raman bands (1648 cm -1 and 1358 cm -1 ) to give and . The intensities are then scaled by the molar concentration of the RhB analyte in the case of the bulk powder v.s. the molecule of a certain concentration deposited on the SERS/PIERS substrates, which is a well-established method to estimate the EF 25,26 . This EF is an underestimate as the likely concentration of the molecule is smaller than that shown as some molecules will not remain bound on the surface or within SERS hotspots.
Eqn. (S1) We thank the reviewer for pointing out these articles -and have modified our introduction to cite several of these works. However, it is the case that the absolute field enhancements obtained by dielectric structures are lower as they do not support the plasmonic gap-modes required for single molecule fluctuation sensing 27 or single molecule strong coupling 28 , and plasmonic nanogaps exceed most reported enhancement factors and are also highly reproducible 29 . But we do agree that more consideration needs to be given to dielectric media for abundance and low cost, which is of interest to the community, and we include a discussion in introduction, along with other low-cost plasmonic metals such as Mg and Al. We have corrected the introduction to highlight the reproducibility of dielectric structures, and the further possibilities achieved when combining them with noble metals: "Many dielectrics can act as passive elements supporting plasmonic metal nanostructures to localize electromagnetic fields via a micro-lensing effect 5 , and providing an inert shell that assists with in-situ SERS measurements (e.g. SHINERS 6 or SPARKs 7 ). Semiconductors may also act as active SERS substrates via charge transfer to the target analyte molecule 8,9 and form reusable SERS substrates through photocatalytic degradation of adsorbed molecules 10 upon exposure to ultraviolet light and are abundant/low cost. These techniques have not achieved single-molecule SERS enhancements generally (EF = 10 2 -10 6 11 ) or work as reproducibly as metal nanoparticle-based SERS 12 . Dielectric SERS 9 remains useful due to its abundance and lower cost, complementing abundant metals such as Mg 13 and Al 14 , and its ability to interrogate chemical reactions 15  6) Supporting Information: Please number SI pages in the following format: "S1, S2…" We thank the editor for pointing these out and have implemented all changes.