Formaldehyde Molecules Adsorption on Zn Doped Monolayer MoS2: A First-Principles Calculation

Based on the first principles of density functional theory, the adsorption behavior of H2CO on original monolayer MoS2 and Zn doped monolayer MoS2 was studied. The results show that the adsorption of H2CO on the original monolayer MoS2 is very weak, and the electronic structure of the substrate changes little after adsorption. A new kind of surface single cluster catalyst was formed after Zn doped monolayer MoS2, where the ZnMo3 small clusters made the surface have high selectivity. The adsorption behavior of H2CO on Zn doped monolayer MoS2 can be divided into two situations. When the H-end of H2CO molecule in the adsorption structure is downward, the adsorption energy is only 0.11 and 0.15 eV and the electronic structure of adsorbed substrate changes smaller. When the O-end of H2CO molecule is downward, the interaction between H2CO and the doped MoS2 is strong leading to the chemical adsorption with the adsorption energy of 0.80 and 0.98 eV. For the O-end-down structure, the adsorption obviously introduces new impurity states into the band gap or results in the redistribution of the original impurity states. All of these may lead to the change of the chemical properties of the doped MoS2 monolayer, which can be used to detect the adsorbed H2CO molecules. The results show that the introduction of appropriate dopant may be a feasible method to improve the performance of MoS2 gas sensor.

Based on the first principles of density functional theory, the adsorption behavior of H 2 CO on original monolayer MoS 2 and Zn doped monolayer MoS 2 was studied. The results show that the adsorption of H 2 CO on the original monolayer MoS 2 is very weak, and the electronic structure of the substrate changes little after adsorption. A new kind of surface single cluster catalyst was formed after Zn doped monolayer MoS 2 , where the ZnMo 3 small clusters made the surface have high selectivity. The adsorption behavior of H 2 CO on Zn doped monolayer MoS 2 can be divided into two situations. When the H-end of H 2 CO molecule in the adsorption structure is downward, the adsorption energy is only 0.11 and 0.15 eV and the electronic structure of adsorbed substrate changes smaller. When the O-end of H 2 CO molecule is downward, the interaction between H 2 CO and the doped MoS 2 is strong leading to the chemical adsorption with the adsorption energy of 0.80 and 0.98 eV. For the O-end-down structure, the adsorption obviously introduces new impurity states into the band gap or results in the redistribution of the original impurity states. All of these may lead to the change of the chemical properties of the doped MoS 2 monolayer, which can be used to detect the adsorbed H 2 CO molecules. The results show that the introduction of appropriate dopant may be a feasible method to improve the performance of MoS 2 gas sensor.

INTRODUCTION
In recent years, two-dimensional (2D) materials have attracted much attention due to their unique physical, chemical and electrical properties (Abbasi and Sardroodi, 2018a;Abbasi and Sardroodi, 2018b;Wu et al., 2018;Abbasi, 2019;Abbasi and Sardroodi, 2019). Among them, monolayer MoS 2 belongs to hexagonal system, which is a typical 2D layered transition metal sulfide with sheet structure similar to graphene (Pan et al., 2020). It has been studied due to the excellent electronic structure, chemical and thermal stability, high surface activity and high strength (Xu et al., 2013). Compared with the zero gap of graphene, single-layer MoS 2 has considerable direct band gap, which is suitable for light emitter, energy conversion and solar cell (Yu et al., 2016). Meanwhile, MoS 2 has large specific surface area, surface activity and excellent adsorption capacity, so it is a special gas storage material or gas sensing material source (Zhang et al., 2017;Zhang et al., 2018;Zhou et al., 2018;Chen et al., 2019;Kathiravan et al., 2019;Tan et al., 2020). These excellent properties make the monolayer MoS 2 have potential applications in the field of gas sensing.
However, due to the lack of free bonds on the surface of intact MoS 2 , which is chemically inert (Wang et al., 2013), the interaction with most gas molecules is limited to physical adsorption (Wanno and Tabtimsai, 2014), resulting in weak interaction between the adsorbent and monolayer MoS 2 , and the change of electronic properties is not obvious, and the original MoS 2 cannot detect H 2 CO gas molecule (Ma et al., 2016a). Therefore, it is an effective and feasible method to adjust the electronic structure, chemical activity and sensitivity of MoS 2 by introducing appropriate dopants into defect sites (Ma et al., 2016c;Sharma et al., 2018;Cui et al., 2019;Guo et al., 2019;Ren et al., 2019;Zhang et al., 2019;Guo et al., 2020;Zheng et al., 2020). For example, Lolla et al. have shown that Fe and Co. doped monolayer MoS 2 can enhance the adsorption of O due to the partial occupation of d-orbitals on Fermi level, and the introduction of doping significantly improves the catalytic activity of MoS 2 monolayer (Lolla and Luo, 2020).  proposed that compared with the original monolayer MoS 2 , N and P doped atoms can enhance the sensing sensitivity of monolayer MoS 2 to O 2 and NO gas molecules . (Sahoo et al., 2016) have shown that the original monolayer MoS 2 is inert to gas molecules such as NH 3 and NO 2 , and the detection sensitivity of antisite doped with MoS 2 for these gas molecules and other chemical substances is significantly improved (Sahoo et al., 2016). Luo et al. have shown that Al, Si and P doped atoms increase the orbital hybridization effect between NO 2 , NH 3 molecules and monolayer MoS 2 , and promote the electron transfer. The doped monolayer MoS 2 has better adsorption performance than the undoped monolayer MoS 2 (Luo et al., 2016). Ma et al. have shown that when Au, Fe, CO and Ni are doped into the monolayer MoS 2 , the charge transfer occurs, the distance between the adsorbed molecule and the dopant is shortened, the adsorption energy is increased, and the gas sensitivity to H 2 , CO, NO and O 2 is increased (Ma et al., 2016b;Kwak et al., 2018;Kwon et al., 2018;Wang et al., 2019a). Au doped monolayer MoS 2 has high charge transfer and strong orbital hybridization ability. Doping Au atoms affect the electronic structure of MoS 2 monolayer, thus improving the adsorption capacity, so that the adsorption structure of C 2 H 6 and C 2 H 4 molecules on Au doped MoS 2 monolayer is relatively stable . In conclusion, although there are some reports on the surface activity of doped monolayer MoS 2 , the adsorption of formaldehyde on the surface of transition metal Zn doped MoS 2 has not been confirmed. Therefore, the geometry, electronic structure and small molecule adsorption of different transition metal atom doped monolayer MoS 2 system can be obtained by theoretical simulation method, which has guiding significance for the study of the unique gas sensing properties, adsorption properties and chemical activities of transition metal atom doped monolayer MoS 2 .
At present, toxic gas molecules are one of the main problems of environmental pollution. H 2 CO is a common toxic gas. H 2 CO is widely used in household materials (Chung et al., 2013;Salthammer, 2013). Long term exposure to H 2 CO will irritate the eyes and throat, make breathing difficult, and even pose a serious threat to the lungs. Therefore, it is of great significance to detect and control H 2 CO in home, residence and scientific research (Lara-Ibeas et al., 2020;Song et al., 2020;Zhou et al., 2020). Based on the first principle calculation, this paper studies the changes of the configuration, geometric stability and electronic structure of MoS 2 substrate caused by the adsorption of H 2 CO on the original and Zn doped monolayer MoS 2 gas after the S vacancy is filled with Zn dopant, and the adsorption energy, adsorption structure and charge transfer of gas molecules are analyzed. This study is helpful to find suitable chemical modification methods to improve the performance of MoS 2 based gas sensors, and has important scientific significance and application prospects for the design of high-efficiency gas sensing materials.

COMPUTING METHOD
All calculations were carried out using the first principle method, which was carried out by Vienna Ab-initio Simulation Package (VASP) and projector enhanced wave (PAW) method of DFT (Qian et al., 2019;Wang et al., 2019b). The configuration of transition metal Zn doped MoS 2 monolayer was optimized. The generalized gradient approximation (GGA) and perdew-Burke-Ernzerhof (PBE) are used to calculate the exchange correlation energy. The C 2s2p, Zn 3d4s and O 2s2p states are regarded as valence electrons. In the process of geometric optimization, all internal coordinates are allowed to relax under a fixed lattice constant, and the energy cutoff for plane waves is set to 450 eV. The Brillouin domain integral uses 3 × 3 × 1 ( Monkhorst and Pack, 1976) monkhorst pack (MP) grid and 0.1 eV Gaussian smear. The convergence criterion is 10 −5 eV. When the force applied to the atom is less than 0.01 ev/Å, the optimized structure is obtained. The calculated lattice constant of MoS 2 is 3.18 Å, which is well consistent with the experimental and theoretical value of 3.20 and 3.18 Å (Ataca and Ciraci, 2011;Le et al., 2014). Dispersive interactions are not included because we are concerned about the effects of chemical bonds and gas molecules on the electronic and magnetic properties of MoS 2 . This method has been used to study gas adsorption on atom doped MoS 2 (Ma et al., 2016a). MoS 2 cell is constructed as a 4 × 4 supercell, in which one S atom is replaced by a Zn doped atom, with a total of 48 atoms, including 16 Mo atoms, 31 S atoms and one Zn atom. In order to avoid the interaction between the MoS 2 monolayer and its periodic image, a vacuum space of 18 Å was added perpendicular to the MoS 2 layer. The binding energy (E b ) between metal atom and support is defined as , where E tot (M + MoS 2 ), E tot (MoS 2 -S) and E tot (M) are the total energy of M/MoS 2 catalyst, energy of MoS 2 vacancy S-based carrier and the energy of single metal atom, respectively. Positive values indicate that the reaction gives off heat. In addition, the adsorption energy (E ads ) was calculated to describe the interaction strength between gas and gas/MoS 2 catalyst. According to the formula E ads E tot (M + MoS 2 ) + E tot (gas) − E tot (gas-M/MoS 2 ), E tot (M + MoS 2 ), E tot (gas) and E tot (gas-M/MoS 2 ) are the energy of M/MoS 2 catalyst, the energy of gas and the total energy of adsorption system respectively. According to this definition, positive adsorption energy represents exothermic adsorption. The density of states (DOS) is calculated by using the K point 5 × 5 × 1 with higher density. The results of DOS were analyzed by P4vasp. Bader charge (Henkelman et al., 2006) was used to analyze the charge transfer. The 3D visualization program Vesta (Momma and Izumi, 2011) was used to visualize all molecular structures, and the electron density difference was obtained to analyze the electron transfer direction. The electron density difference is defined as △ρ , ρ M/MoS2 and ρ gas represent the electron density of adsorption system, M/MoS 2 catalyst and gas, respectively. The PAW results based on VASP processing and the COHP diagram of LOBSTER 4.0.0 (Local Orbital Basis Suite Towards Electronic-Structure Reconstruction) (Maintz et al., 2016) were used to analyze the bonding.

Properties of Zn Doped Monolayer MoS 2 (Zn-MoS 2 )
Seen from Supplementary Figure S1A, nine possible adsorption sites were considered for H 2 CO adsorb on the original MoS 2 surface, where T S , T Mo1 /T Mo2 , H 1 /H 2 and B 1 /B 2 /B 3 represent the top of S and Mo atoms, hexagonal ring center and bridge sites. The T SV represent the top site of Zn doped the S vacancy. As depicted in Supplementary Figure S1B, the band structure and total density of states (TDOS) of the original monolayer MoS 2 show that the original MoS 2 monolayer is a non-magnetic semiconductor with a direct band gap of 1.74 eV, which is well consistent with the results reported in the literature value of 1.74 eV (Dimple et al., 2017). The calculated binding energy of Zn doping on MoS 2 surface is 0.5 eV, which indicates that this structure is easy to form under thermodynamic equilibrium conditions due to the exothermic process. As shown in Figure 1B, the charge accumulation and loss can be observed in both Zn and Mo atoms, which means that chemical bonds are formed between Zn and Mo atoms in the ZnMo 3 clusters, which can be used as a new surface single cluster catalyst (SCC) (Ma et al., 2018) to study the adsorption performance of H 2 CO molecules. For the average bond length between Zn dopant and adjacent Mo atoms, the calculated average bond length of Zn-Mo is 2.65 Å, which is larger than that of S-Mo bond in original monolayer MoS 2 with the value of 2.41 Å. As exhibited in Figure 1A, accordingly the expansion of Zn-Mo bond relative to S-Mo bond makes the doped Zn atom protrude 0.26 Å above the S-plane. The electron transfer between dopant and MoS 2 is calculated by Bader charge analysis. The trend of charge transfer is consistent with that of element electronegativity (Allred, 1961). The paulin electronegativity of Mo is 2.16, which is greater than that of Zn (1.65). Accordingly, Zn dopant loses electrons and carries a positive charge of 0.35 e. The charge distribution of Zn-MoS 2 can be confirmed from Figure 1B. It is easy to see that Zn atoms are surrounded by cyan, which indicates that Zn atoms lose electrons. In addition, the magnetic moment of MoS 2 is produced by Zn doping, the total magnetic moment of the single-layer MoS 2 is 2.00 µ B , only 0.1µ B is located on the doped Zn atom, which indicates that the magnetic moment of the system mainly comes from Mo atom. In order to further understand the electronic and magnetic properties of Zn-MoS 2 , the total DOS (TDOS) and projected DOS (PDOS) of Zn-MoS 2 spin polarization are given in Figure 1C. It can be seen from Figure 1C that an asymmetric DOS peak appears near the Fermi level, which is obviously different from the perfect MoS 2 monolayer. This is consistent with the fact that the Zn-MoS 2 system is paramagnetic (2.0 µb). Compared with MoS 2 monolayer Supplementary Figure S1B, the spin down channel of Zn-MoS 2 maintains the zero gap semiconductor characteristics of MoS 2 , but the spin up channel presents a non-zero density of states near Fermi level which indicates that the Zn-MoS 2 system is semimetallic. Seen from the PDOS shown in Figure 1C, the degree of spin asymmetry of the 4d orbit of Mo is greater than that of the 3d orbit of Zn. This is consistent with the fact that the magnetic moment is mainly located on Mo atoms near Zn doping. In addition, since the asymmetric DOS peak is dominated by the 4d orbit of Mo, it can be expected that the spin charge density is mainly distributed on Mo atoms. Therefore, as shown in Figure 1B, the spin charge density of Zn-MoS 2 system is mainly concentrated around Mo atom. In addition, Figure 1C also shows that near the Fermi level, the 3p state of Zn atom is hybridized with the 4d orbital of Mo, indicating the interaction between metal atom and S-vacancy.

Adsorption of H 2 CO on Original MoS 2 Monolayer
In order to obtain a stable configuration, various possible initial adsorption structures were considered Supplementary Figure  S1A. The interaction between H 2 CO and original MoS 2 is very weak, and the stable configuration obtained belongs to physical adsorption. In this work, only the configuration with the largest and most stable adsorption energy is discussed. The adsorption energy, charge transfer and other related parameters are shown in Table 1, and the geometric electronic structure is shown in Figure 2.
Seen from Figure 2A, the adsorption energy of H 2 CO on the original monolayer MoS 2 is 0.04 eV. The adsorption of H 2 CO is almost perpendicular to the plane, and the H-end is downward. The nearest distance between the molecule and the substrate is 3.13 Å. Due to the small adsorption energy, the interaction between the adsorbed molecules and the substrate is weak, and the geometric structure of the adsorbed molecules is almost undisturbed. The C-O bond length is about 1.21 Å, and C-H bond length is about 1.12 Å, which is the same as that of H 2 CO bond in gas phase Figure 2A. The position of S atom under the adsorbed H 2 CO does not change, and the bond length between S and Mo is still 2.41 Å. This result can also be confirmed by Figure 2B where H 2 CO is almost surrounded by cyan, and only 0.01 e was obtained from the original monolayer MoS 2 . In order to further understand the interaction between the adsorbed H 2 CO and the original monolayer MoS 2 , we also calculated the TDOS of S/H 2 CO structure and the DOS of H 2 CO before and after adsorption, as shown in Figure 2C. After the adsorption of H 2 CO, we can see that there is no induced impurity state, and the band gap has no obvious change. Just because of the introduction of molecules, the single peak increases, indicating that the adsorption almost does not change the electrical properties of the original monolayer MoS 2 , It is well consistent with the literature report (Ma et al., 2016b). In other words, the original monolayer MoS 2 is not sensitive to H 2 CO, which further proves that the adsorption of H 2 CO on the original monolayer MoS 2 belongs to physical adsorption.

Adsorption of H 2 CO on Zn Doped Monolayer MoS 2 (Zn/H 2 CO)
Finally, four stable configurations of H 2 CO adsorption structure on Zn-MoS 2 were obtained, including Zn/H 2 CO-(a), Zn/H 2 CO-(b), Zn/H 2 CO-(c) and Zn/H 2 CO-(d). The structure parameters are shown in Figure 3, and the other related parameters are shown in Table 1.

Configuration of the Adsorbed Zn/H 2 CO-(a) and Zn/ H 2 CO-(b)
As shown in Figure 3A,B, the adsorption energies of Zn/H 2 CO-(a) and Zn/H 2 CO-(b) are 0.98 and 0.80 eV, respectively. The distance between the O atoms of the adsorbed molecule and Zn dopant is 1.98 and 1.95 Å, respectively, indicating that the TABLE 1 | Parameters of stable configuration of H 2 CO adsorbed on original and Zn doped monolayer MoS 2 : adsorption energy (E ad in eV), charge obtained by H 2 CO (Q g in e), charge obtained by Zn (Q Zn in e), magnetic moment of Zn atom (M Zn in µ B ), nearest distance between adsorbed molecule and Zn atom (d g-Zn in Å), average distance between Zn atom and its adjacent molybdenum atom (d s/Zn-Mo in Å), The height of Zn atom relative to S plane (h in Å). For M (μ B ), the values inside and outside the brackets are the magnetic moment of the adsorbed molecule and the magnetic moment of the whole cell, respectively. It should be noted that S/H 2 CO refers to the configuration shown in Figure 3A, and the dopant of this configuration is actually S atom.  Figures 4A,B to further understand the interaction between H 2 CO molecule and Zn doped monolayer MoS 2 . The yellow area is the electron accumulation area, and the cyan area is the electron consumption area. As shown in Figure 4A, the electron transfer is not only located on the C and O atoms of H 2 CO adsorption, but also on the O-Zn bond, which is consistent with the strong adsorption capacity of H 2 CO. In addition, the loss of electrons on the C-O bond leads to the weakening of the C-O bond, which makes the O atom protruding above the S plane chemically active to other molecules, including H 2 CO itself. For the adsorption of Zn/H 2 CO-(b), it can be found that the adsorption behavior is similar to that of Zn/H 2 CO-(a), as shown in Figure 4B, which will not be further discussed.

CO-(a) and Zn/H 2 CO-(b) is shown in
In order to further understand the adsorption behavior of H 2 CO on Zn-MoS 2 surface. Figures 5A-D displayed the spinpolarized total densities of states (TDOS) (upper panels) and corresponding DOS projected on 3d states of Zn atom, adsorbed H 2 CO gas molecules and the isolated H 2 CO gas molecules (lower panels) after H 2 CO adsorption on Zn-embedded monolayer MoS 2 .
The TDOS of Zn/H 2 CO-(a) and Zn/H 2 CO-(b) systems are shown in Figures 5A,B. Compared with Zn-MoS 2 , due to the hybridization of Zn atoms and H 2 CO molecules, the charge is transferred from the matrix to the adsorbed H 2 CO molecule, resulting in a new DOS peak at CBM for the TDOS of Zn/H 2 CO-(a) and Zn/H 2 CO-(b) systems. It can be observed that the occupied state PDOS of the adsorbed H 2 CO molecule Figures  5A,B, below is much lower panels than Fermi level, and the induced impurity state is produced, which reveals the reaction between Zn-MoS 2 monolayer and H 2 CO molecule. For Zn/ H 2 CO-(a) and Zn/H 2 CO-(b) configurations, the molecular orbitals of adsorbed H 2 CO are delocalized relative to the isolated H 2 CO in the gas phase. The 3d orbital of Zn atom is coupled with H 2 CO in the range of 9.60∼0.00 eV. The interaction between H 2 CO molecule and Zn atom leads to charge transfer. Zn/H 2 CO-(a) and Zn/H 2 CO-(b) structures have higher adsorption energy, which indicates that the adsorption is  Figures 6A,B that when H 2 CO is adsorbed to Zn-MoS 2 , there are a small amount of O-Zn bonding orbitals (-COHP values) at Fermi level, and the orbitals above Fermi level belong to anti bonding orbitals. In other words, the O-Zn bond is enhanced after H 2 CO adsorption, which is consistent with the increase of C-O distance ( Figures 4A,B). The O atoms in the two adsorption systems have strong binding with Zn atoms (ICOHP value is small), which also shows that these phases are stable.  Compared with H 2 CO in the gas phase, the geometry and substrate of the adsorbed state are only slightly changed. The C-O bond of H 2 CO decreased by 0.01 Å. In addition, for Zn/H 2 CO-(c) and Zn/H 2 CO-(d), there is a small electron transfer (0.07 and 0.08 e) between the adsorbed H 2 CO and the substrate, and the molecule has a small magnetic moment of 0.01 µ B . The adsorption of Zn/H 2 CO-(c) and Zn/H 2 CO-(d) is weaker than that of Zn/H 2 CO-(a) and Zn/H 2 CO-(b), indicating that the probability of occurrence of the latter two configurations is much higher than that of the former two. For the adsorption of Zn/H 2 CO-(c) and Zn/H 2 CO-(d) configurations, the charge density difference diagram shows that there is almost no electron accumulation between the adsorbed molecule H 2 CO and the Zn doped MoS 2 monolayer ( Figures 4C,D). It is further confirmed that the adsorption capacity of H 2 CO on the substrate is weak, which is consistent with the small adsorption energy and large distance mentioned above.
Further analyzing the adsorption behavior of H 2 CO on the Zn-MoS 2 surface, it can be seen from Figures 5C,D above that the TDOS of the Zn/H 2 CO-(c) and Zn/H 2 CO-(d) systems do not show induced impurity state near the Fermi level, and the DOS curves of the adsorbed H 2 CO of the Zn/H 2 CO-(c) and Zn/H 2 CO-(d) systems overlap slightly with the 3d orbitals of the Zn atoms ( Figures 5C,D,  below), shows that the interaction between H 2 CO and Zn-MoS 2 is weak, the bonding between H-Zn atoms is weak, and the ICOHP negative value is large ( Figures 6C,D), resulting in only 0.07 and 0.08 e being transferred from the adsorbed H 2 CO molecule to the final substance. The H-Zn strength in Zn/H 2 CO-(c) system is higher than that in Zn/H 2 CO-(d) system, indicating that Zn/H 2 CO-(c) system is more stable than Zn/H 2 CO-(d) system. This conclusion is consistent with the previous calculation of adsorption energy ( Table 1). In terms of magnetic properties, the total magnetic moment of the whole adsorption system did not change after adsorption of H 2 CO by Zn-MoS 2 (Zn/H 2 CO-(c) and Zn/H 2 CO-(d) were 2.00 µ B ), which was consistent with the small adsorption energy of Zn/H 2 CO-(c) and Zn/H 2 CO-(d).

CONCLUSION
In conclusion, according to the first principles calculations, we have studied the effects of Zn doping S vacancy on the electronic structure, magnetic properties and chemical activity of monolayer MoS 2 . The calculation of binding energy shows that Zn atoms are closely bound to S-defects, which is mainly due to the hybridization between dopant atoms and their nearest Mo  atoms. Finally, a new single cluster catalyst on ZnMo 3 surface is formed, which improves the selectivity of MoS 2 surface. By embedding Zn atoms, the magnetic properties of MoS 2 monolayer can be adjusted and the spin magnetic moment of Zn-MoS 2 is 2.00 µ B . The electronic properties of MoS 2 are also changed by the impurity states induced in the band gap. The effects of H 2 CO adsorption and doping on the chemical activity of MoS 2 monolayers were further investigated. It was found that the H-end downward adsorption of H 2 CO in the original monolayer MoS 2 and Zn doped monolayer MoS 2 was very weak, and the electronic structure of the two substrates changed little after adsorption, indicating that the two systems were not sensitive to H 2 CO.When the O atom in H 2 CO molecule faces to the substrate, the adsorption capacity is strong, and the adsorbed H 2 CO is effectively activated. DOS analysis showed that the electronic structure of Zn-MoS 2 could be changed by introducing impurities in the band gap when the O-terminal of H 2 CO molecule was adsorbed downward. At the same time, the magnetic properties of Zn-MoS 2 system are also adjusted. The COHP diagram shows that Zn atoms are strongly bonded with O atoms. This study shows that Zn doping is a promising method to optimize the electronic structure, magnetic properties and chemical activity of MoS 2 , which provides a promising way to improve the electronic properties of MoS 2 materials.

DATA AVAILABILITY STATEMENT
The original contributions presented in the study are included in the article/Supplementary Material, further inquiries can be directed to the corresponding authors.