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Insights into the degradation of diphenhydramine – An emerging SARS-CoV-2 medicine by UV/Sulfite

As Diphenhydramine (DPH) has been considered as a drug to treat SARS-CoV-2, the degradation of DPH from water was investigated and evaluated in this study by adopting an advanced oxidation/advanced reduction process – the UV/sulfite process. The UV/sulfite system was able to eliminate DPH within 6 mins under UV254nm and 1.0 mM sulfite. It was observed that the presence of NO3-, NO2-, Cl-, HCO3-, and SO42- anions in water can affect the performance of UV/Sulfite degradation system. The mechanism of UV/sulfite/anions was evaluated which the presence of NO3- in UV/sulfite process has revealed faster initial decay rate but lower final DPH removal. It was observed that the UV/Sulfite process was extremely sensitive to pH as the dissociation of ion species varied among pH. The reaction became sluggish in acidic solution due to the dissociation of less reactive species such as HSO3-. In alkaline solution, SO32- was the dominant species, producing powerful SO3∙- and eaq- when activated by UV at 254 nm. By conducting LC/MS analysis, the degradation pathway was proposed and can be summarized into four main pathways: hydroxylation, side chain cleavage, losing aromatic ring or ring opening. Scavenging tests were also carried out and validated the presence of various radicals contributing to the reaction, including eaq-, H˙, OH˙, SO3˙-, O2•- and SO4˙-.


Introduction
The COVID-19 caused by SARS-CoV-2 has led to a global health concern and safe drugs for prevention have been an urge to for protecting vulnerable populations. It has been reported that antihistamine has a high potential to alleviate the symptoms caused by SARS-CoV-2 [1]. Diphenhydramine -a widely used over-the-counter antihistamine as the form of diphenhydramine hydrochloride (DPH) to relieve symptoms of allergy and common cold, has been discovered by an in vitro study to exhibit direct antiviral property against SARS-CoV-2 and the usage of diphenhydramine can reduce the positivity of SARS-CoV-2 in older subjects [2]. With the hope of using diphenhydramine for disease prevention, early intervention or therapy of COVID-19, extensive use of diphenhydramine could cause disaster to the aquatic ecosystem when discharged if they are not treated correspondingly. Although the detected concentration of pharmaceuticals and personal care products (PPCPs) are relatively low (less than1 μg/L) [3], they are persistent in the environment and can affect the metabolisms and biology of most aquatic lives. It has been reported that around 2-15 % of DPH are excreted unmetabolized and the removal of antihistamines like DPH in municipal wastewater treatment plants is only 69 % [4]. Among many kinds of pharmaceuticals discharged to the environment, DPH is one of them that has been specifically identified in major streams 0.01 to 0.10 μg/L [5,6], soil (20 -50 μg/kg) [6], and fish tissue in multiple studies [7][8][9]. According to Du, Price, Scott, Kristofco, Ramirez, Chambliss, Yelderman and Brooks [4], the n-octanol water partition coefficient of DPH (logK ow = 3) was significantly higher among other water contaminants and the presence of DPH in municipal wastewater influence has exhibited huge seasonal difference which the concentration was significantly greater in fall (530 to 600 µg/L) then winter (160 to 180 µg/L).
The exposure of streams ecosystems to DPH can cause a reduction of 61 % in respiration and 99 % in photosynthesis [3]. It has been found that DPH could be photodegraded under sunlight in the presence of humic substances with half-lives of 5.4 h and is inactivated in 200 days using anaerobic biological treatment [10,11]. In order to facilitate DPH removal in wastewater treatment plant, a more efficient method is proposed for DPH removal.
Previous studies of DPH removal in different photo-reactors by UV-C/H 2 O 2 showed that total removal can be achieved under 150 mg/L of H 2 O 2 in 60 min, while only 10 % of Total Organic Carbon (TOC) was removed [12]. Fenton process is also a common process to remove such pharmaceuticals in wastewater. It is reported that in dosages of 15 mg/L and 2.5 mg/L of H 2 O 2 and Fe 2+ , 60 % of DPH is removed in 60 min, where the removal was increased with increasing dosages of reactants [12]. However, such total removal required excessive dosage of H 2 O 2 and Fe 2+ , which could generate secondary pollution in effluent. Therefore, heterogeneous catalysis for DPH removal was considered. TiO 2 with UV-A was studied and around 50 % removal was achieved [12]; Adsorption of DPH was studied on swelling clay, activated carbon and aluminosilicates [13][14][15]. However, the adsorption process is rather slow, often required several hours to reach the equilibrium. To achieve faster reaction and better removal, advanced oxidation and reduction were examined.
Sulfate radicals (SO 4 -) and hydroxyl radicals (ȮH) have been widely applied as an oxidant under common advanced oxidation processes (AOPs) due to the high oxidation potential (2.5 -3.1 V vs NHE and 1.8 -2.7 V vs NHE respectively) [16]. The convenient production of SO 4 and ˙O H are generated by activation of peroxymonosulfate (PMS), persulfate (PS) or peroxydisulfate (PDS) via UV, heat, ultrasound, electrochemical means [17][18][19][20][21], where the process can be assisted or catalyzed using transition metals [21]. Although the efficiency of AOPs is high, there are some drawbacks such as the high concentration of PMS or PDS residuals in the treated wastewater [22,23]. PS and PMS have been reported to have acute toxicity, which could pose other hazards and induce secondary pollution [24,25]. Thus, an Advanced Reduction Processes (ARPs) by activating sulfite to generate highly reductive radicals has been proposed as an alternative method [26]. Comparing with PMS and PDS, sulfite has been considered as a cheap, efficient, and eco-friendly chemical for the degradation of emerging organics. The activation could be done by UV, high energy electron beam (HEEB), ultrasound and microwave [27]. It has been reported that the application of heavy metal -Co (III) for the activation of sulfite may contribute to significant drawbacks such as the leaching of heavy metals into water [28]. Nonetheless, the direct activation by UV irradiation was found to be the most effective method for persistent compounds [29,30]. Thus, the application of UV to activate sulfite has been proposed by previous studies as a green technology to degrade emerging pollutants in water [16].
UV/sulfite process has demonstrated excellent performance on the removal of organic pollutants and heavy metals by providing exclusive reducing and oxidizing agents [31,32]. It has been reported that the photolysis of sulfite can generate reductive species such as hydrated electrons (e − aq , − 2.9Vvs.NHE), Hydrogen radical (H • , − 2.3Vvs.NHE) and sulfite anion radicals (SO 3 •− , 0.63 − 0.84 V) [33][34][35]. The e − aq has been reported as a nucleophile that can react with organic molecules by attaching to aromatic rings or substituting one electron on alkene double bonds [36]. Meanwhile, it has been demonstrated that the SO 3 •− can further dissociate with dissolved oxygen (DO) in water to produce extra oxidizing agents (SO 5 -, SO 4 and ˙O H) which can initiate AOPs [37][38][39][40].
Despite the high efficiencies for both AOPs and ARPs, the studies on the discovery of this ARP/AOP hybrid system was currently limited. Thus, the aim of this study is to examine the performance of UV/sulfite for the removal of DPH, as well as investigating the synergetic effects of combined AOP/ARP. Various parameters were investigated for process optimization and the degradation mechanisms were studied via the identification of the reaction pathways.

Chemicals and reagents
All chemicals are analytic reagent grade and all solvents and HPLC or LCMS grade and were used as received without further purification. Diphenhydramine Hydrochloride (99 %, C 17 H 22 ClNO) was purchased from Acros Organics, USA. Sodium Sulfite (98 %, Na 2 SO 3 ) was purchased from BDG Laboratory Supplies, England. Acetonitrile, Methanol and Na 2 S 2 O 3 (99 %) where purchased from Duksan. NaOH and HCl were used for pH adjustment and were purchased from Sigma-aldrich. Anions (Na 2 SO 4 , NaHCO 3 , NaNO 2 , NaNO 3 and NaCl) were purchased from Riedel-deHaen.

Experimental procedures
The photodegradation was carried out in a UV reactor installed with three UV lamps and a mixer. The experimental setup is shown in Fig. S1. The UV lamps were turned on 20 min prior the experiment to ensure stable UV light intensity. The mixer was in fixed position to ensure homogeneity throughout the reaction process. The pH of reaction mixture was adjusted by HCl or NaOH. 750 uL of sample was extracted from the suspension in specific operating time interval and was immediately quenched by 250 μL of methanol. For TOC measurement, 8 mL of sample was mixed with 12 mL of sodium thiosulfate quencher to prevent any interference.

Analytical methods
The concentration of DPH in samples were quantified by HPLC consisting of a Waters 2487 pump and a Waters Symmetry column (4.6 × 150 mm, 5 μm particle size), with a flow rate of 1.0 mL/ min with 80 μL injection volume. The detection wavelength was set at 220 nm. The mobile phase was a mixture acetonitrile and water at 60:20 (v/v) with 0.1 % phosphoric acid. TOC measurement was performed using TOC-L analyzer purchased from Shimadzu TOC 5000A equipped with an ASI-5000A autosampler. The identification of reaction intermediates was conducted by Thermo Scientific Orbitrap Fusion Lumos Mass Spectrometer with ESI ion source at both positive and negative mode. The Orbitrap resolution is 120,000 and scan range is 50-500 m/z. The chromatography was conducted with a Waters Dionex UltiMate 3000 RSLCnano. The mobile phase is a mixture of A: water and B: acetonitrile. The gradient progressed linearly from 95 % A to 5 % from 0 to 9 min, and maintained at 5 % for 2 mins, and returned to initial condition in 0.5 min and maintained for 3 mins. The flow rate was 0.3 mL/min and the whole program lasts for 15 mins.

Effect of UV wavelengths
Two sets of experiments were conducted under different wavelengths with same initial [DPH] at 0.05 mM with and without sodium sulfite to reveal the effect of direct photolysis and UV/sulfite at different UV wavelengths and the result is shown in Fig. 1. In general, experiments with sodium sulfite performed better than direct photolysis where 254 nm/sulfite has the best performance among all, with complete removal in 6 min. Without sulfite, the removal of DPH by direct photolysis was very limited. For 254 nm, the removal of DPH by direct photolysis is around 15 %, which is noticeably higher than 300 and 350 nm (5 % and 1 %). This is because shorter wavelength can provide higher photon energy which more SO 3 •− can be activated from sulfite.
With the addition of sulfite, the removal of DPH at 300 nm and 350 nm has only increased slightly (5 % and 8 % respectively). However, the removal of DPH has reached 100 % at 254 nm which is significantly better then UV 300 and UV 350 . Despite the higher photon energy provided at 254 nm, it has been demonstrated that the molar extinction coefficient of sulfite is significant only at wavelength below 260 nm [41]. Moreover, the absorptivity of sulfite has been reported to drop from 3.0 to zero when wavelength is greater than 260 nm [42]. Thus, the activation of sulfite by UV at 300 nm and 350 nm are very limited. The significantly better performance of UV 254 /sulfite can be attributed to both improved photolysis and the efficient activation of sulfite to produce reactive radicals for DPH degradation as shown in Eq. (1) -(5) [38][39][40]43]. Apart from the production of SO 3 •− and e − aq by photolysis, Since UV 254 /sulfite has a desirable performance on DPH degradation, this process was selected for other experiments in this study.

Effect of sulfite dosage
To evaluate the influence of sulfite on DPH degradation, different dosages of sodium sulfite ranging from 0.1 to 5.0 mM were tested as shown in Fig. 2. From [Sulfite] 0 0.1 to 1.0 mM, the degradation rate and removal increased linearly. Both the reaction rate and removal are optimal at [Sulfite] 0 = 1.0 mM. According to the decay rate constants at different [sulfite] 0 , a linear relationship was proposed when [sulfite] 0 is less than 1.0 mM (Eq. (6)). The increase in SO 3 2supply could lead to more production of reactive radicals such as e − aq and SO 3 •via Eq. (6) for DPH degradation. However, when [sulfite] 0 is further increased beyond its optimal, a decline in reaction rate and removal was observed. One possible explanation for this phenomenon is that an overdose of sulfite could hinder the average UV light intensity adsorbed by the solution [44], where the activation of sulfite could be reduced. Apart from the blockage of UV light, the self-scavenging effect of SO 3 •can also hinder the reaction as less radicals are available for reaction (Eq. (7) -(8)) [45]. It is also reported that e − aq can form an adduct with sulfite ions (Eq. (9)) [46], reducing the amount of e − aq for reaction. To minimize the scavenging effect, the concentration of sodium sulfite added to the reaction should be controlled to maintain the optimal sulfite radical quantity. In this case, [sulfite] 0 = 1.0 mM was adopted for all the other tests.

Effect of anions
It has been reported that the photochemical activities of inorganic anions in water may affect the removal of organics in UV/sulfite system [35,47]. The anions that can influence the UV/sulfite system include NO 3 − , NO 2 − , Cl − , HCO 3 − , and SO 4 2− . Thus, these anions were selected in this study to evaluate their effect on UV/sulfite process. As shown in Fig. 3a -3b, only the addition of NO 3 − have positive effect on the UV/sulfite process, resulting in a faster initial decay rate (k = 0.138 min − 1 ). However, the final removal of DPH was then hindered after 10 min. The increase of initial rate could be due to the photolysis of NO 3 − which extra oxidizing agents O( 3 P) and HO • generated (Eq. (10) -(12)). The reduced DPH removal could be due to the NO 3 − scavenging effect on e − aq which reduced the overall reactive species in the system (Eq. (13)).
To further elaborate the effect of NO 3 − on DPH degradation, different dosages of NO 3 − (10 mM, 30 mM, and 60 mM) were examined under both UV/sulfite process and direct photolysis ( Fig. 3c -3d). According to Fig. 3c, increasing the dosage of NO 3 − to 60 mM has neither increased the initial decay rate, nor hindered the final removal comparing with 10 mM dosage. This means that the production of reaction species (Eq. (10) -(12)) and reduction of reaction species (Eq. (13)) is approaching equilibrium, which higher dosage will not significantly increase nor reduce functional reaction species. According to    (17) -(18)) to form other products with NO • or NO − 2 , which will significantly reduce the HO • produced. Moreover, NO − 2 has been reported to be an e − aq scavenger as shown in Eq. (19) [48]. This will reduce the reaction species in UV/sulfite system which resulted in strong process retardation. Comparing with Cl − anions, the impact of also exhibited the ability to reduce the overall performance of UV/sulfite process.

Effect of DPH dosage
The effect of initial DPH concentration was tested from 0.005 mM to 0.100 mM DPH as shown in Fig. 4a. Complete removal was achieved with DPH initial concentration lower than 0.010 mM. As the detected environmental DPH in stream is less than 0.0004 μM, the system is found to be useful for environmental DPH treatment. The removal and reaction rates decrease with increasing DPH concentration, suggesting that the sulfite is the liming factor, where the competition between DPH and radicals increases with [DPH] 0 . Moreover, the increase in [DPH] 0 causes more production of intermediate compounds, which will also lead to competition for radicals, causing even slower reaction. For accurate prediction of the reaction performance, the correlation between the first order rate constant k and 1/[DPH] 0 is shown in Fig. 4b and is expressed as Eq. (22). The equation shows a straight-line correlation, indicating

Effect of initial pH under UV 254 /Sulfite
The initial pH of the reaction solution is an important parameter for UV/sulfite degradation process as pH can affect the dominant species and the pathway of DPH removal. The initial pH level from 2.56 to 10.99 were studied under the UV 254 /sulfite system. The results were shown in Fig. 5a b and the dissociation of ion species varies at different pH are predicted and presented in Fig. 5c. According to Fig. 5a, it was noted that the optimum pH value for the removal of DPH was 10.04, which pH adjustments was required to achieve desired pH values for this system. The reaction rate in acidic pH (i.e. pH 2.7 to 5.6) was sluggish where only less than 30 % of DPH were removed within 30 min. According to Fig. 5b, although the optimum pH was observed to be 10.04, the pH during reaction was constant through the reaction. Instead, the pH has a significant drop at pH 5.12 to 7.86 which indicated that acidic reaction intermediates were tending to be produced under a more neutral condition. This is because the dissociation of H • was the highest at pH 5.12 to 7.86 which can promote hydrogenation of intermediates to form -COOH compound. A summary of the reactions under acidic pH is listed in Table 1.
It was observed that the reaction rate and removal efficiency was significantly improved in alkaline pH condition comparing with acidic environment. This could be due to the variation on molar absorptivity of sulfite under UV irradiation with pH. It has been demonstrated that an increase in pH from 3 to 7 can cause the absorptivity to increase for more than 12 folds and further pH increment results in linear increase in absorptivity [27], such that the UV activation is more favorable at high pH.
Apart from the variation of molar absorptivity, the reaction was retarded at lower pH as the abundant H + in the acidic solution causes scavenging effect on e − aq (Eq. 23) at k = 2.3 × 10 10 M − 1 s − 1 [46], such   that less e − aq are available for reaction. It has been reported that the concentration of e − aq is at least 4 to 5 times more in pH 9 than pH 4 -5 [50]. According to Fig. 5c, at pH less than 7.2, SO 3 2- (Eq. 26 -27), once again reducing the available e − aq for reaction. Altogether, the degradation by SO 3 •− and e − aq is hindered at lower pH, and since the removal is similar to photolysis presented earlier, the removal pathway at acidic pH is proposed to be solely direct photolysis.
At alkaline pH, the reaction is notably faster as the dissociation of SO 3 2-(Eq. 24) is favored at pH higher than the pKa of DPH (pKa = 8.87), which resulted in more available SO 3 2for activation. It has been reported in previous study that at pH higher than 9, 98 % of sulfite are in the form of SO 3 2- [52], indicating that SO 3 2is the dominant species in alkaline pH.
At this stage, the synergetic effect of combined advanced oxidation and reduction (AOP/ARP) was observed. The AOP/ARP process can provide extra degradation pathway for DPH including hydroxylation, cleavage of alkylate side chain and loss of aromatic ring, resulting at a much better performance than in lower pH. Thus, the optimum for this reaction will occur at pH 10.04 as the production of SO 4 •and SO 5 •is favored.
According to Fig. 5c, the dissociation of e − aq (Eq. 23) can reach 100 % at pH 10.04 which can contribute to the notable increase in reaction rate as the standard reduction potential of e − aq (E • = − 2.77 V) is higher than H • (E • = − 2.42 V) [55]. The e − aq can also reacts with dissolved oxygen to form another radical, O 2 •-(Eq. 28) [56], which is proposed to contribute considerably to the increased rate. Apart from that, the DPH will be protonated to form DPH + ions with pH > pKa (Eq. 29), which can also contribute to faster degradation of probe compound. The reactions involved in alkaline solution are summarized in Table 2.
To further elaborate the impact of pH on DPH degradation with UV and sulfite in aqueous condition, the degradation of DPH by solely photolysis (Fig. S2a), solely sulfite (Fig. S2b) and solely hydrolysis ( Fig. S2c) under various pH was examined. The results indicated that the reaction would be retarded at neutral pH for the three comparative tests which indicated that the dissociation of e − aq and DHP + would affect the UV/sulfite process more significantly. In short, the UV/sulfite system for DPH degradation is significantly more efficient in alkaline pH due to physical (molar absorptivity, quantum yield), chemical (dissociation of desired ions at higher pH) properties and the combined effects of AOP/ ARP.

Role of radical species in the UV/sulfite system
As the activation of sulfite can be achieved by adopting UV 254 irradiation, leading to the generation of the sulfite anion radicals (SO 3˙-), aqueous electron (e − aq ), and other oxidizing radicals (SO 4 •-& OH˙) under aerobic conditions (Eq. (2) -(3)) [38,54,57]. Therefore, it is vital to investigate the dominating reactive species for the DPH degradation in the UV 254 /sulfite process. To examine the reaction mechanism, different types of scavengers were added to the reactions. Five types of scavengers, NO 2 -, NO 3 -, methanol, butanol and nitrogen purging were added into separate solutions as shown in Fig. 6. It is concluded that except for NO 3 -, the addition of all other four kinds of scavengers caused a decline in removal in different degrees. The order of retardation in terms of reaction rate is summarized as NO 2 Interestingly, the removal of oxygen via nitrogen purging did not cause a complete retardation, where only 38 % of decline in the degradation efficiency was observed. It is anticipated that the production of powerful reactive species such as SO 4 •and OH • will be hindered in the absence of oxygen (Eq. (2) -(3)), implying that the DPH degradation can be achieved using SO 3 •and/or e aq -. The addition of NO 3 did not cause a notable effect on the degradation efficiency, which is unexpected due to the high capability of NO 3 to scavenge e − aq (Eq. (13)) [26,49]. Instead, the presence of NO 3 - [26,59,60]. Conversely, the reactivity of SO 3 •and SO 5 •was reported to be low toward methanol and Table 2 Reactions in alkaline pH.

Reactions
Favorable pH/ pKa Eq , OH • and e − aq are the dominate reactive species responsible for the DPH decay in the UV 254 /sulfite process suggesting the synergistic effect of both advanced reduction and advanced oxidation processes.

DPH degradation pathways
As illustrated in Scheme 1, a series of DPH degradation intermediates formed from the UV photolysis of sulfite were traced and identified by the UPLC-ESI-MS system. All the intermediates were verified by comparing their obtained experimental m/z values with the corresponding mass spectrum in the LC/MS library (Table S1). Based on this technology, the DPH degradation was elucidated through four major pathways, including hydroxylation (A1-A4), cleavage of alkylamine side chain (B1-B6), loss of aromatic ring (C1-C5), and open of aromatic ring (D1-D4). These reaction products are considered to be involved in multiple chain reactions, which could be first being oxidized, then reduced, or vice versa.
Firstly, the hydroxylation was mediated by the OH • radical addition on the aromatic ring with the loss of H • to form A1, as OH • are expected to be reactive towards electron rich aromatic systems by adducting on the meta-, ortho-, and para-positions [61]. The mono-hydroxylation further increased the electron-rich property of phenyl ring, making it more readily to be di-hydroxylated [62]. While the addition of OH • radicals on the other non-hydroxylated phenyl ring is another preferred way, which leads to the production of two mono-hydroxylated aromatic ring within a DPH molecule. Both constitutional isomers were grouped as intermediate A2. Likewise, A2 underwent a series of oxidation from the attack of reactive radicals to generate tri-hydroxylated A3 and tetrahydroxylated A4, accordingly [63]. Secondly, the cleavage of alkylamine side chain is another possible way for DPH decay in the UV photolysis of sulfite. It was initiated by hydroxylation on different positions of alkylamine chain to give the birth of derivatives B1. The further oxidation occurred on different hydroxylated sites of B1 via Habstraction reaction with OH • and subsequently formed ketonic product B2 with several isomers. Afterwards, B3 was originated from a demethylation effect at N-C bond. B4 was assigned to the product of deamidation by e aq -/SO 3 •reaction with amine group from B2 and the scission of amino group from B3. Further oxidation took place on B2 or B4 to yield diphenylmethanol (B5) through the dissociation of benzyl or the break of ketone group, respectively. The benzophenone fragments (B6) was emerged by the further transformation of B5 based on Habstraction of e aq -/SO 3 •- [64]. Thirdly, as a parallel degradation route, DPH was found to loss one aromatic ring, yielding the derivative C1 which conserves single phenyl ring. Two isomers of derivative C2 could be assigned according to the OH • radical electrophilic adduction on the alkylamine chain. The ketonic products (C3) were subsequently generated attributed to the H-abstraction on the hydroxyl group [65]. Further oxidation resulted in the scission of side chain on C3, generating C4 and C5 accordingly. Fourthly, the opening of aromatic ring in DPH structure was observed in the UV/sulfite process through the breakage of C--C bond in π orbitals, which give the birth of derivative D1 [66]. With the further attack of OH • radicals, it is expected that the aliphatic chain of D1 was hydroxylated first and followed by the H-abstraction to produce ketonic structure D2 and D3, resulting in the scission of aliphatic chain. Carboxylation product was also observed from converting D3 to D4.

Conclusion
This study examined the mechanism of UV 254 /sulfite for DPH degradation, and the process was able to achieve complete removal in 6 min under desirable pH levels. The pH level of solution was discovered to have greatly influenced the dominant species accounting for degradation. In summary, at lower pH, the reaction is hindered due to the dissociation of ineffective HSO 3 -, while at higher pH, SO 3 2is the prevailing species, leading to the surge of reactive SO 3

•-
, SO4˙-and e − aq , which contributed to the much faster degradation. The scavenging test has revealed that DPH can be degraded through both advanced oxidation and advanced reduction processes, where mainly SO 3 -, SO 4 •-, OH • and e − aq contributed to the degradation. It is discovered that among the five scavengers used, NO 3 caused an increase in reaction rate due to the generation of an extra radical. The anions presented water will cause negative effect to the process. LCMS was also conducted to study the reaction pathway, and DPH was found to degrade into smaller molecules by H-abstraction, hydroxylation, side chain cleavage, losing aromatic ring or ring opening.

Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Data availability
Data will be made available on request.