Anion-adaptive crystalline cationic material for 99TcO4− trapping

Efficient anion recognition is of great significance for radioactive 99TcO4− decontamination, but it remains a challenge for traditional sorbents. Herein, we put forward a tactic using soft crystalline cationic material with anion-adaptive dynamics for 99TcO4− sequestration. A cucurbit[8]uril-based supramolecular metal-organic material is produced through a multi-component assembly strategy and used as a sorbent for effective trapping of TcO4−. Excellent separation of TcO4−/ReO4− is demonstrated by fast removal kinetics, good sorption capacity and high distribution coefficient. Remarkably, the most superior selectivity among metal-organic materials reported so far, together with good hydrolytic stability, indicates potential for efficient TcO4− removal. The structure incorporating ReO4− reveals that the supramolecular framework undergoes adaptive reconstruction facilitating the effective accommodation of TcO4−/ReO4−. The results highlight opportunities for development of soft anion-adaptive sorbents for highly selective anion decontamination.

c, a long-lived (t 1/2 = 2.13 × 10 5 y) radioisotope of technetium, is an abundant and problematic nuclear waste component and potent radioactive pollution source 1,2 . Complex chemical behavior of 99 Tc hampers separation of uranium and plutonium during reprocessing of spent nuclear fuel, and high volatility of 99 Tc species (Tc 2 O 7 ) constrains incorporation into glass waste forms via high-temperature vitrification. 99 Tc, as a stable TcO 4 − in its dominant + 7 oxidation state, is highly water soluble and can migrate readily in the environment, thereby posing severe environmental risks. Therefore, efficient capture of radioactive 99 Tc has received considerable attention for both nuclear waste management and contaminant remediation purposes.
Solvent extraction and ion exchange are two well-established effective methods for removal of TcO 4 − from aqueous media [3][4][5][6] . In solvent extraction, extractants with anion recognition capability can achieve high selectivity for TcO 4 − 4,7-9 , but practical applications are limited by cost and inefficiency. Ion exchange is developed as an alternative of traditional extraction. Despite the ease of implementation and the expected efficient recovery of TcO 4 − based on ion-exchange method 5,10 , the total performance of sorbent materials used seems not to be competent. For example, most traditional polymeric materials exhibit slow anion exchange kinetics and poor radiation resistance 11,12 , while inorganic cationic materials such as layered double hydroxide (LDH) 13 , sulfides 14 , and borates 15,16 exhibit low sorption capacity and poor selectivity. The emergence of hydrolytically stable cationic metal-organic materials (MOMs) has led to potent applications for capture of oxyanion pollutants 3,[17][18][19][20] . High porosity, structural diversity, and functional tunability [21][22][23] render these hybrid materials as promising candidates for TcO 4 − removal 24,25 . However, there is still demand for improvement in terms of selectivity of TcO 4 − sorbents, with enhanced discrimination for TcO 4 − /ReO 4 − over other anions as a particularly desirable attribute.
There is no doubt that anion receptors 7,9,[26][27][28][29] of TcO 4 − have the best ion selectivity. A rational approach for improving the selectivity of solid sorbents is to give sorbent materials an ideal ion-recognition capability by direct functionalization of traditional solid sorbents with covalently attached anion receptors ( Fig. 1a) 30,31 , but unfortunately, chemical modification method generally suffers from the necessity for elaborate syntheses and possible deactivation of functional recognition groups after implanting in bulk materials. Herein, inspired by molecular recognition of anion receptors, we put forward an alternative tactic that circumvents this drawback via an easily prepared anion-adaptive sorbent material that can behave like an anion receptor itself (Fig. 1b) [32][33][34][35][36] . Conceptually, this soft sorbent material is capable of dynamically tuning the structural arrangement of its framework in response to different anions, enabling attainment of an optimized pore size and shape match for maximum interactions with, and the resulting selectivity for target anions such as TcO 4 − . Specifically, the desirable anionadaptive sorbent material should have two crucial attributes of structural dynamics and anion-responsive capability, which can be easily achieved in self-organization-based supramolecular materials bearing recognition sites 37,38 . Glycoluril derivatives containing abundant -CH or -CH 2 motifs as potent anionrecognition sites, among which endo-type bambusurils can serve as anion receptors [39][40][41] , while exo-type cucurbiturils exhibit anion-binding affinity through outer-surface interaction (Fig. 1c), can be used to prepare a class of anion-adaptive cationic materials for specific anion removal [42][43][44][45] . A multicomponent assembly strategy is proposed for synthesizing such sorbents based on a versatile glycoluril-based macrocyclic host, cucurbit [8]uril (CB8). The CB8 macrocycle used here plays a vital role in accomplishing both the construction of a supramolecular network [46][47][48] and anion recognition (Fig. 1d), and endows both important attributes mentioned above: (a) abundant CH and CH 2 groups on its waist for outer-surface hydrogen-bonding recognition to promote the TcO 4 − capture; (b) flexibility of the CB8 encapsulation motif allowing dynamics of the overall supramolecular framework 49-51 . In this work, a CB8-based cationic supramolecular metalorganic framework, SCP-IHEP-1 ([Cu((bpy) 2 @CB8)(H 2 O) 4 ] (NO 3 ) 2 ·18H 2 O), is constructed by the supramolecular collaborative assembly. As expected, this material is demonstrated to be an efficient and selective sorbent capable of reversibly sequestrating TcO 4 − /ReO 4 − by trapping them in specific tetrahedral pores created by CB8 moieties arranged in order. The anion-adaptive capability of this supramolecular sorbent toward effective TcO 4 − recognition resembles the dynamic behavior of the receptor during ion recognition, and can be taken as a representative TcO 4 − -specific smart sorbent material.

Results
Assembly of SCP-IHEP-1 based on CB8. The cationic supramolecular framework material, SCP-IHEP-1, was synthesized via assembly of CB8, 4,4′-bipyridine (bpy) and Cu(NO 3 ) 2 under hydrothermal conditions. It crystallizes in monoclinic space group P2 1 /n (Supplementary Table 1) as pale blue block crystals (Supplementary Figure 1). Crystal structure of SCP-IHEP-1 reveals that all the four components (CB8, bpy, Cu 2+ , and NO 3 − ) (Supplementary Figure 2) are included during the self-assembly process, and the main building unit of the supramolecular framework of SCP-IHEP-1 (Fig. 2a) is a one-dimensional (1D) metal-organic polyrotaxane chain (Fig. 2b) based on encapsulation motif, 2bpy@CB8, linked by Cu 2+ (Fig. 1c). Given the potential for competition between metal coordination and supramolecular encapsulation of bpy, one-pot synthesis of SCP-IHEP-1 having both types of connectivities for bpy suggests stepwise assembly, with initial supramolecular encapsulation of bpy in CB8 followed by assembly into a 1D chain via bpy-Cu 2+ coordination (Supplementary Figure 3). This assembly mechanism was corroborated by an alternative two-step method in which isolation of the dimeric bpy units encapsulated in CB8, 2bpy@CB8, in the form of [(bpy) 2 @CB8] 0.5 · [(bpy) 2 @CB8] 0.5 ·19H 2 O (Supplementary Figure 4 and 5) is followed by assembly with the metal ions provided as Cu(NO 3 ) 2 . It is notable that, whereas 2G@H encapsulation, where G denotes a guest molecule, and H a host, is common for host CB8 [46][47][48]52 , this motif is rare for neutral guest such as bpy in CB8 53 . Actually, formation of 2bpy@CB8 in aqueous solution involves a large favorable enthalpy change as a result of release of high-energy water (Supplementary Figure 6 and Supplementary Table 2), which should be taken as the main driving force for this encapsulation 54,55 and results in different degrees of pi-pi stacking (Supplementary Figure 4) and a variety of hydrogen bonds between CB8 and bpy (Supplementary Figure 7 and Supplementary Table 3).
Cationic 1D polyrotaxane chains in SCP-IHEP-1 can further assemble into a three-dimensional (3D) supramolecular framework via cross-linkage of a large number of interchain hydrogen bonds (Supplementary Figure 8 and Supplementary Table 4). The nitrate counterions are located in tetrahedral cavities formed by four neighboring CB8 from the 1D chains (Fig. 2d, e and Supplementary Figure 9), and also contributed a lot to the formation of final supramolecular framework via anion-directed assembly (Fig. 2f). Analysis of the local nitrate anion environment reveals its interaction with only two CB8 macrocycles of the tetrahedral cavity through a limited number of hydrogen bonds (Supplementary Figure 10), suggesting weak interaction with main 1D backbones of SCP-IHEP-1 and the potential for exchange with oxyanions having more favorable interactions, such as TcO 4 − /ReO 4 − .
In contrast, coordination assembly simply from bpy and Cu (NO 3 ) 2 in the absence of CB8 macrocycles results in a twofold interpenetrating 3D framework based on six-coordinated copper nodes with deformed octahedral geometry (namely as Cu-bpy, see Supplementary Table 1 and Supplementary Figure 11). In addition to the nitrate directly binding to a copper center, there should be a disordered nitrate anion in the pore of 3D framework to balance the charge.
After exposure of SCP-IHEP-1 crystals for 12 h at 298 K to aqueous solutions with pH values ranging from 3 to 11, the structure as determined by powder X-ray diffraction (PXRD) remained essentially unchanged (Fig. 3a). The results suggest thermal and hydrolytic stability, despite the flexible supramolecular framework. Meanwhile, in contrast to significant dehydration of Cu-bpy at low temperatures (Supplementary Figure 12), SCP-IHEP-1 did not undergo any significant decomposition until over 205°C (Fig. 3b), suggesting its high thermal stability.
Sorption performance for ReO 4 − removal. ReO 4 − was initially used as a nonradioactive structural analog of 99 TcO 4 − to assess anion exchange of SCP-IHEP-1. Batch kinetics experiment shows that removal of ReO 4 − by SCP-IHEP-1 follows the pseudo-firstorder model (Supplementary Figure 13 and Supplementary  Table 5), and is achieved to 88% removal at 1 min and to over 95% after 10 min (Fig. 4a). The fast kinetics of ReO 4 − exchange by SCP-IHEP-1 is superior to those of other cationic metal-organic materials such as SLUG-21 20 , UiO-66-NH 3 +17 ,

Glycoluril-based Precursor
and Ni(II)-based MOF 19 , all of which take over 24 h to reach exchange equilibrium for sequestering ReO 4 − . It is notably that, SCP-IHEP-1 also shows faster removal rate and much higher removal ratio than its CB8-free counterpart Cu-bpy (an equilibrium time of 30 min and a final removal ratio of 20%, Supplementary Figure 14 and Supplementary Table 6).
As revealed by the sorption isotherm experiment (Fig. 4b), the calculated maximum sorption capacity of SCP-IHEP-1 based on the Langmuir model is 157 mg Re g −1 sorbent corresponding to 211 mg ReO 4 − g −1 sorbent (Supplementary  Figure 15 and Supplementary Table 7), which is higher than those for LDH (130 mg ReO 4 − g −1 ) 13 , NDTB-1 (49 mg 16 , and UiO-66-NH 3 + (159 mg ReO 4 − g −1 ) 17 . Assuming that all the nitrate ions can be exchanged, the sorption capacity of SCP-IHEP-1 for ReO 4 − observed here reaches to as high as 93% of the theoretical value (226 mg g −1 ), suggesting its nearly perfect exchange tendency for ReO 4 − . Moreover, the distribution coefficient (K d ) of SCP-IHEP-1 toward ReO 4 − is 2.6 × 10 5 mL g −1 (Supplementary Table 8), which is also comparable to recently emerging highperformance cationic MOFs, SCU-100, and SCU-101 (Table 1) 24,25 , and ensures the decontamination depth of ReO 4 − . In contrast, ReO 4 − removal by CB8-free Cu-bpy can only achieve a poor separation efficiency (K d :~1 × 10 3 mL g −1 , Supplementary Table 8), which is two orders of magnitude lower than that of SCP-IHEP-1. Correspondingly, the derived maximum sorption capacity of 138 mg ReO 4 − g −1 (Supplementary Figure 16 and Supplementary Table 9) only reaches 14%  (Fig. 4d). Although ReO 4 − removal diminishes somewhat when competing with structurally similar ClO 4 − , it remains as high as 91% (Supplementary  Table 11). Under similar conditions, ReO 4 − removal by SCU-101 24 does not exceed 90%, and removal by PAF-1-F 56 is only ca. 20% in the presence of SO 4 2− or PO 4 Given the high concentration of nitrate ion in high level nuclear waste stream, the competing effect of excess nitrate anions is critical during TcO 4 − removal. Moreover, for certain types of nuclear waste, high-concentration SO 4 2− is also another potent competing anions. Therefore, ReO 4 − removal with higher concentrations of competing NO 3 − and SO 4 2− were further studied to check the uptake selectivity of ReO 4 − . As shown in Fig. 3e, removal of ReO 4 − remains as high as 96% for a molar ratio of NO 3 − to ReO 4 − of 20:1, and is 84% for a ratio of 100:1 (Supplementary Table 12). Remarkably, an increase in SO 4 2− has little effect on the uptake of ReO 4 − (Fig. 3f), with removal falling only from 98 to 92% when the SO 4 2− :ReO 4 − ratio increases from 1:1 to 4000:1 (Supplementary Table 13).
Removal selectivity of SCP-IHEP-1 toward TcO 4 − /ReO 4 − can be partially ascribed to its inherent feature of inorganic-organic hybrid material based on multi-component collaborative assembly. Generally, anions with higher charge density such as SO 4 2− often have better uptake than those with lower charge density (TcO 4 − /ReO 4 − ) during the sorption process with inorganic anion sorbents 13,15,16 . However, this order always is reversed for organic polymers and inorganic-organic hybrid materials, which is taken as a Hofmeister phenomenon 57 . This Hofmeister behavior might be originated from the hydrophobic nature of organic backbones of these materials, as evidenced by the methylene/methylidyne-rich tetrahedral pores of SCP-IHEP-1. 3 A similar trend is observed for other MOMs bearing local hydrophobic cavities or pores 24,25,58 . That is to say, considering the differences in hydration energy of anions, the preference for larger poorly hydrated ReO 4 − anions over NO 3 − or SO 4 2− reflects the important role of hydration/dehydration in the anion exchange, which is consistent with the exothermic feature of exchange observed above.
TcO 4 − removal from simulated nuclear wastes. The overall selectivity of SCP-IHEP-1 toward ReO 4 − against NO 3 − and SO 4 2− observed here is better than those of MOF-typed (SCU-101) 25 and polymeric network-typed (SCU-CPN-1) 57 anionic exchange materials with excellent ReO 4 − /TcO 4 − removal performance emerging recently, making it a promising candidate for selective sequestration of TcO 4 − from waste solutions, even in the presence of high concentration of competing anions. To assess the potential application of SCP-IHEP-1 in real nuclear solutions containing radioactive TcO 4 − , removal experiments for TcO 4 − were also tested. Uptake kinetics of TcO 4 − by SCP-IHEP-1 is as fast as that of ReO 4 − , achieving~80% removal at 1 min and over 90% after 10 min (Fig. 5), and nearly quantitative removal after 2 h. In a simplified simulated waste stream containing 9.8 ppm 99 TcO 4 − in 0.03 M HNO 3 (i.e., a NO 3 − concentration~500 times higher than TcO 4 − ), although the TcO 4 − removal is affected by the high-concentration competing NO 3 − , the removal percentage of TcO 4 − is still up to 79.2% using a solid-to-liquid ratio (SLR) of 0.5, which is superior to the removal by SCU-100 (59.3% with a SLR of 1.0) 25 and SCU-101 (75.2% with a higher SLR of 10) 24 and represents the best removal performance for 99 TcO 4 − among cationic MOMs reported so far.
Mechanism for selective ReO 4 − uptake. ReO 4 − (and by inference TcO 4 − ) exchange of SCP-IHEP-1 was monitored by Fourier transform infrared spectroscopy (FTIR) (Fig. 6a), PXRD patterns (Fig. 6b), and energy dispersive X-ray spectroscopy (EDS) (Fig. 6c). Single crystals of ReO 4 − incorporated material (SCP-IHEP-1-Re) were also obtained and subject to X-ray diffraction structural determination on the Beijing Synchrotron Radiation  Table 3). The crystal structure of SCP-IHEP-1-Re reveals close-packing mode similar to SCP-IHEP-1 but with a change of stacking orientation originated from its single-crystal-to-single-crystal (SCSC) transformation upon ReO 4 − incorporation (Fig. 7a). Compared to the coordination environment of NO 3 − in SCP-IHEP-1, encapsulation of ReO 4 − is achieved by the rearrangement of surrounding CB8 moieties with a resulting slight deformation of the tetrahedral pores (Fig. 7b). The above results indicate that the removal of TcO 4 − /ReO 4 − by SCP-IHEP-1 is mainly attributed to anion-adaptive reorganization of the CB8-based pores, which can dynamically adapt to the encapsulated anionic guest. A comparison of this CB8-based MOM sorbent material with Cu-bpy or other CB8-free MOM sorbents material such as SLUG-21 20,41 and SBN 58 reveals that the removal of TcO 4 − / ReO 4 − by SCP-IHEP-1 leads to little structural change of supramolecular framework, while anion removal by the latter ones rely on coordination of target anions with metal centers accompanied by irreversible significant structural arrangement (Supplementary Figure 24). Evidently, the inherent flexibility of soft supramolecular framework of SCP-IHEP-1 facilitates a fast dynamic recognition process, and thus enables superior kinetics as well as good reversibility of anion exchange. Especially, the involvement of CB8 macrocycles in SCP-IHEP-1 plays a vital role in directing supramolecular assembly process, and can be indeed an important contributor to high selectivity in terms of constructing ordered pores for anion trapping and interacting with trapped anions through a mass of hydrogen bonds. The fast kinetics, reversibility and selectivity as well as high efficiency by this type of soft supramolecular material make it outcompetes with traditional cationic MOM sorbents.
In order to understand the driving force underlying the specific ReO 4 − /TcO 4 − uptake, theoretical calculation methods were used to analyze the interactions of CB8-based host cationic framework with different anions (NO 3 Supplementary Table 15. These values are in the range 0.02 < ρ < 0.07 e/Å 3 , 0.2 < ∇ 2 ρ < 0.8 e/Å 5 , 4.5 < G < 18.3 kJ/mol/Bohr 3 , −15.7 < V < -3.1 kJ/mol/ Bohr 3 , respectively. For shorter H-Bond lengths (e.g., 2.511 Å), these values are within the scope of weak hydrogen bonding, while the larger ones belong to van der Waals interactions [61][62][63] . These intermolecular interactions can be further detected by independent gradient model (IGM) 64 analysis and reduced density gradient (RDG) 65 analysis (Fig. 8 and Supplementary  Figure 29 and 30), and proved be weak hydrogen bonding (lightblue area in isosurfaces) and van der Waals interactions (green area in isosurfaces). The results are in excellent agreement with the QTAIM analysis. Besides, the low-density and   Table 16). Further energy analysis shows that difference of anion-[H] binding energies (ΔBE gas ) for all these three models are not significant, whilst the difference of hydration energy (ΔE hyd ) between ReO 4 − and NO 3 − is dominant. This result suggests the vital role of hydrophobic nature of CB8-based methylene/methylidyne-rich tetrahedral pores of SCP-IHEP-1 in selective TcO 4 − /ReO 4 − removal, and thus provides a valuable evidence for the Hofmeister bias selectivity of SCP-IHEP-1 mentioned before.

Discussion
We put forward a tactic using anion-adaptive cationic material with structural dynamics for 99 TcO 4 − sequestration. As a conceptual prototype, a soft supramolecular material, SCP-IHEP-1, was synthesized and has been demonstrated to exhibit excellent removal performance of TcO 4 − (and ReO 4 − ), especially in selectivity against competing anions. This exceptional performance is attributed to the anion-adaptive rearrangement of the CB8-surrounded pores, which can adapt to the encapsulated anionic guest. Hydration energy difference between displaced NO 3 − and target oxoanions should be the essential driving and ReO 4 − (blue represents a strong attraction, and red denotes a strong repulsion). All isosurfaces are colored according to a BGR (blue-green-red) scheme over the electron density range −0.05 < sign(λ 2 )ρ < 0.05 a.u force for facilitating selective TcO 4 − uptake of sorbents with hydrophobic pores. The result suggests the potential of this anion-adaptive cationic material SCP-IHEP-1 for effective TcO 4 − removal, and most importantly, paves a way for developing high efficiency sorbents for anion removal based on soft sorbent materials with anion-adaptive dynamics and efficient anion recognition capability to achieve selective and specific anion binding.

Methods
Materials. Caution! Tc-99 possesses significant health risks when inhaled or digested and should be handled according to standard precautions and procedures. All Tc-99 studies were conducted in a licensed laboratory dedicated to radiological investigations. Cucurbit [8]uril (CB8) was synthesized according to the previously-reported literature 66 Figure S4) and 1 H-NMR spectra ( Figure S5). 1  After slowly cooling to room temperature in a period of 24 h, the obtained blue regular plate-like crystals of Cu-bpy were filtered, rinsed with water three times, and dried in air at room temperature. Yield: 0.013 g.
Synthesis of SCP-IHEP-1-Re. To elucidate the exchange and recognition mechanism for SCP-IHEP-1 with ReO 4 − (and by inference TcO 4 − ), crystals of ReO 4 − -incorporated SCP-IHEP-1 sorbent were synthesized through an in situ assembly method. The detailed synthesis procedure is as follows: 0.2 M Cu(NO 3 ) 2 aqueous solution (200 μL, 0.04 mmol) and 0.2 M NH 4 ReO 4 aqueous solution (400 μL, 0.04 mmol) was added to a suspension of 2bpy@CB8 obtained as described above in water (2 mL) in a stainless-steel vessel. The mixture was sealed, and kept at 150°C for 48 h. After cooling to room temperature, small light-blue prismatic crystals of SCP-IHEP-1-Re were obtained. The PXRD pattern of SCP-IHEP-1 after ReO 4 − uptake collected is fully consistent with the simulated PXRD pattern based on crystal data for SCP-IHEP-1-Re obtained above, suggesting identical structures.
Synthesis of Cu-bpy-Re. An aliquot of 0.2 M Cu(NO 3 ) 2 aqueous solution (500 μL, 0.10 mmol) and 0.2 M NH 4 ReO 4 aqueous solution (400 μL, 0.04 mmol) was added to a suspension of 4,4′-bipyridine (bpy) (0.006 g, 0.04 mmol) in water (2.0 mL) in a stainless-steel vessel. The mixture was sealed, and heated slowly to 150°C in a period of 24 h, and kept at 150°C for another 48 h. Blue block crystals of Cu-bpy-Re were obtained after slowly cooling to room temperature in a period of 24 h.
X-ray single-crystal structure determination. X-ray diffraction data for SCP-IHEP-1, Cu-bpy, and Cu-bpy-Re were acquired on a Bruker D8 VENTURE X-ray CMOS diffractometer with a Cu Kα X-ray source (λ = 1.54178 Å) at room temperature. Data frames were collected using the program APEX 3 and processed using the program SAINT routine in APEX 3. Data collection for 2bpy@CB8 and SCP-IHEP-1-Re was acquired with synchrotron radiation at Beijing Synchrotron Radiation Facility (BSRF, λ = 0.72 Å) using a MAR CCD detector. The crystal was mounted in nylon loops and cooled in a cold nitrogen-gas stream at 100 K. Data were indexed, integrated and scaled using DENZO and SCALEPACK from the HKL program suite. All crystal structures were solved by means of direct methods and refined with full-matrix least squares on SHELXL-97 67 , and refined with fullmatrix least squares on SHELXL-2014 67,68 . The crystal data of all compounds are given in Supplementary Table 1.
Batch experiments. All the sorption experiments were conducted using the batch sorption method. The solid/liquid ratio performed in all batch experiments was 0.5 g L −1 . In a typical experiment, 4 mg of SCP-IHEP-1 or Cu-bpy was added into 8 mL of aqueous solution with a certain concentration of ReO 4 − . The pH values of the solutions were adjusted as required using NaOH and HNO 3 and were measured on a digital pH-meter. The mixture was stirred for a specified time (t, min) at a specified temperature (T, K), and separated with a 0.22 μm nylon membrane filter. The concentrations of ReO 4 − in aqueous solution were determined by inductively coupled plasma optical emission spectrometry (ICP-OES, Horiba JY2000-2).

Data availability
Details for measurements and characterization, detailed experimental procedures, computational methods are given in the Supplementary Methods. The X-ray crystallographic coordinates for structures reported in this study have been deposited in the Cambridge Crystallographic Data Center under accession numbers CCDC: 1874188 (2bpy@CB8), 1874189 (SCP-IHEP-1), 1874190 (SCP-IHEP-1-Re), 1894900 (Cu-bpy), and 1894899 (Cu-bpy-Re), respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif). All data are either provided in the Article and its Supplementary Information or available from the corresponding author upon request.