Polymeric ISE for Hydrogen Sulfite Based on Bis‐Urea Calix[4]diquinones as Neutral Lipophilic Ionophores

A new PVC membrane electrode for HSO₃^? anion based on bis‐urea calix[4]diquinones I–VI as neutral ionophores is prepared. Of the various membranes prepared, the membrane based on calix[4]diquinone III exhibits a linear stable response over a wide concentration range (6.0×10^?5?1.0×10^?2) with a slope of ?51.5 mV/decade and a detection limit of 2.2×10^?6 M. With the exception of HSO₃^? anion, the remainder of the anions responds based on their hydrophobicity. The membrane revealed improved selectivity coefficients for HSO₃^? over a wide variety of other anions, and the comparable selectivity for the HSO₃^?selective membranes is iodide anion.     

Products of the oxidation of 1‐(diaminomethylene)thiourea with hydrogen peroxide

Two oxidation products of 1‐(diaminomethylene)thiourea (HATU) are reported, obtained from reactions with hydrogen peroxide at two different concentrations; these are 3,5‐diamino‐1,2,4‐thiadiazole, C₂H₄N₄S, (I), related to HATU by intramolecular N—S bond formation, and 1‐(diaminomethylene)uronium hydrogen sulfate, C₂H₇N₄O⁺·HSO₄⁻, (II). In (I), molecular hydrogen‐bonded chains could be distinguished, further organized in a herring‐bone‐like pattern. The structure of (II) is stabilized by an extensive network of N—H...O and O—H...O hydrogen bonds, where hydrogen‐bonded anion chains and characteristic cation–anion motifs are present. The compounds are of importance not only with respect to crystal engineering, but also in the design of new synthetic routes to HATU transition metal complexes.     

Synthesis of Pyrazolo[3,4‐d]pyrimidin‐4‐ones Catalyzed by Br?nsted‐acidic Ionic Liquids as Highly Efficient and Reusable Catalysts

A convenient and efficient method for the synthesis of pyrazolo[3,4‐d]pyrimidin‐4‐ones via heterocyclization reaction of 5‐amino‐1H‐pyrazole‐4‐carboxamides with triethyl orthoesters using two Br?nsted‐acidic ionic liquids, 3‐methyl‐1‐(4‐sulfonic acid)butylimidazolium hydrogen sulfate [MIM⁺(CH₂)₄SO₃H][HSO₄^?] or N‐(4‐sulfonic acid)butyl triethylammonium hydrogen sulfate [Et₃N⁺(CH₂)₄SO₃H][HSO₄^?], as efficient homogeneous catalysts under solvent‐free conditions is described.     

An oxonium hydrogen sulfate of 3a,6a‐diphenyl­glycoluril

In the title compound, (5‐oxo‐3a,6a‐diphenyl­perhydro­imidazo[4,5‐d]imidazol‐2‐ylidene)oxonium hydrogen sulfate, C₁₆H₁₅N₄O₂⁺·HSO₄⁻, the asymmetric unit contains a hydrogen sulfate anion and a 3a,6a‐diphenyl­glycoluril oxonium cation. The hydrogen sulfate anion is joined to the oxonium cation via a strong O—H⋯O hydrogen bond (H⋯O = 1.69 Å). The crystal packing is mainly dominated by inter­actions involving the hydrogen sulfate anion. The diphenyl­glycoluril oxonium cations also self‐assemble through N—H⋯O hydrogen bonds, forming mol­ecular chains along the [001] vector. Four intra­molecular C—H⋯N hydrogen bonds are observed, having an S(5) motif.     

Mono Halogen Substituted Calix[4]pyrroles: Fine-tuning the Anion Binding Properties of Calix[4]pyrrole

Abstract

Single halogen atom (i. e. I, Br, Cl and F) substituted calix[4]pyrroles, compounds 2, 3, 4 and 5, were synthesized. Studies of these systems reveal that replacement of a single β-pyrrolic hydrogen atom can increase the anion binding ability of calix[4]pyrroles for a variety of anions (e. g. Cl^?, Br^?, H₂PO₄ ^? and HSO^? ₄) relative to normal non-halogen substituted calix[4]pyrrole 1. In the case of chloride anion, the expected relative affinity sequence of 5 > 4 > 3 > 2 was observed. This was not found to be true for Br^?, H²PO^? ₄, and HSO^? ₄. Here, the chlorine substituted calix[4]pyrrole 4 was found to display a slightly higher affinity in the case of each anion than the fluorine-bearing derivative 5. This was rationalized in terms of intermolecular NH … F hydrogen bonding interactions being present in CD₂Cl₂ solutions of 5. Support for this latter conclusion came from concentration and temperature-dependent NMR spectroscopic studies.

A matched set of mono halogen substituted calix[4]pyrroles was used to study in detail, the extent to which halogen substituents may be used to fine-tune the anion binding properties of calix[4]pyrroles.     

Dual Role of the 1,2,3‐Triazolium Ring as a Hydrogen‐Bond Donor and Anion–π Receptor in Anion‐Recognition Processes

Several bis(triazolium)‐based receptors have been synthesized as chemosensors for anion recognition. The central naphthalene core features two aryltriazolium side‐arms. NMR experiments revealed differences between the binding modes of the two triazolium rings: one triazolium ring acts as a hydrogen‐bond donor, the other as an anion–π receptor. Receptors 9²⁺?2BF₄ ^? (C₆H₅), 11²⁺?2BF₄ ^? (4‐NO₂?C₆H₄), and 13²⁺?2BF^4? (ferrocenyl) bind HP₂O₇^3? anions in a mixed‐binding mode that features a combination of hydrogen‐bonding and anion–π interactions and results in strong binding. On the other hand, receptor 10²⁺?2 BF₄ ^? (4‐CH₃O?C₆H₄) only displays combined Csp₂?H/anion–π interactions between the two arms of the receptors and the bound anion rather than triazolium (CH)⁺???anion hydrogen bonding. All receptors undergo a downfield shift of the triazolium protons, as well as the inner naphthalene protons, in the presence of H₂PO₄^? anions. That suggests that only hydrogen‐bonding interactions exist between the binding site and the bound anion, and involve a combination of cationic (triazolium) and neutral (naphthalene) C?H donor interactions. Theoretical calculations relate the electronic structure of the substituent on the aromatic group with the interaction energies and provide a minimum‐energy conformation for all the complexes that explains their measured properties.     

Formation of the bisulfite anion (HSO3–, m/z 81) upon collision‐induced dissociation of anions derived from organic sulfonic acids

In the negative‐ion collision‐induced dissociation mass spectra of most organic sulfonates, the base peak is observed at m/z 80 for the sulfur trioxide radical anion (SO₃^–·). In contrast, the product‐ion spectra of a few sulfonates, such as cysteic acid, aminomethanesulfonate, and 2‐phenylethanesulfonate, show the base peak at m/z 81 for the bisulfite anion (HSO₃^–). An investigation with an extensive variety of sulfonates revealed that the presence of a hydrogen atom at the β‐position relative to the sulfur atom is a prerequisite for the formation of the bisulfite anion. The formation of HSO₃^– is highly favored when the atom at the β‐position is nitrogen, or the leaving neutral species is a highly conjugated molecule such as styrene or acrylic acid. Deuterium‐exchange experiments with aminomethanesulfonate demonstrated that the hydrogen for HSO₃^– formation is transferred from the β‐position. The presence of a peak at m/z 80 in the spectrum of 2‐sulfoacetic acid, in contrast to a peak at m/z 81 in that of 3‐sulfopropanoic acid, corroborated the proposed hydrogen transfer mechanism. For diacidic compounds, such as 4‐sulfobutanoic acid and cysteic acid, the m/z 81 ion can be formed by an alternative mechanism, in which the negative charge of the carboxylate moiety attacks the α‐carbon relative to the sulfur atom. Experiments conducted with deuterium‐exchanged and deuterium‐labeled analogs of sulfocarboxylic acids demonstrated that the formation of the bisulfite anion resulted either from a hydrogen transfer from the β‐carbon, or from a direct attack by the carboxylate moiety on the α‐carbon. Copyright © 2012 John Wiley & Sons, Ltd.     

Porous Molybdenum‐Based Hybrid Catalysts for Highly Efficient Hydrogen Evolution

We have synthesized a porous Mo‐based composite obtained from a polyoxometalate‐based metal–organic framework and graphene oxide (POMOFs/GO) using a simple one‐pot method. The MoO₂@PC‐RGO hybrid material derived from the POMOFs/GO composite is prepared at a relatively low carbonization temperature, which presents a superior activity for the hydrogen‐evolution reaction (HER) in acidic media owing to the synergistic effects among highly dispersive MoO₂ particles, phosphorus‐doped porous carbon, and RGO substrates. MoO₂@PC‐RGO exhibits a very positive onset potential close to that of 20 % Pt/C, low Tafel slope of 41 mV dec^?1, high exchange current density of 4.8×10^?4 A cm^?2, and remarkable long‐term cycle stability. It is one of the best high‐performance catalysts among the reported nonprecious metal catalysts for HER to date.     

Evidence for ion–ion interactions between peptides and anions (HSO4− or ClO4−) derived from high‐acidity acids

The existence of gas‐phase electrostatic ion–ion interactions between protonated sites on peptides ([Glu] Fibrinopeptide B, Angiotensin I and [Asn¹, Val⁵]‐Angiotensin II) and attaching anions (ClO₄^? and HSO₄^?) derived from strong inorganic acids has been confirmed by CID MS/MS. Evidence for ion–ion interactions comes especially from the product ions formed during the first dissociation step, where, in addition to the expected loss of the anion or neutral acid, other product ions are also observed that require covalent bond cleavage (i.e. H₂O loss when several carboxylate groups are present, or NH₃ loss when only one carboxylate group is present). For [[Glu] Fibrinopeptide B + HSO₄]^?, under CID, H₂O water loss was found to require less energy than H₂SO₄ departure. This indicates that the interaction between HSO₄^? and the peptide is stronger than the covalent bond holding the hydroxyl group, and must be an ion–ion interaction. The strength and stability of this type of ion‐pairing interaction are highly dependent on the accessibility of additional mobile charges to the site. Positive mobile charges such as protons from the peptide can be transferred to the attaching anion to possibly form a neutral that may depart from the complex. Alternatively, an ion–ion interaction can be disrupted by a competing proximal additional negatively charged site of the peptide that can potentially form a salt bridge with the positively charged site and thereby facilitate the attaching anion's departure. Copyright © 2014 John Wiley & Sons, Ltd.     

Anion Recognition Using Novel and Colorimetric Tweezer Receptors:1,3-Phenylenedi(carbonylhydrazone) in Aqueous-organic Binary Solvents

本文设计合成了2种新型的间苯二甲酰腙类钳形受体。在DMSO和DMSO-H2O混合溶液中,通过紫外可见光谱分别考察了受体分子3a对F-, Cl-, Br-, I-, AcO-, HSO4-, H2PO4-和ClO4-的相互作用。结果表明,在DMSO溶液中,受体3a对F-,CH3COO-和H2PO4-有显著识别效果,溶液颜色由无色变为黄色,实现裸眼检测。在15%H2O-85%DMSO含水体系中,3a可高选择性识别CH3COO-。1H NMR滴定表明过量F-的加入使受体分子3a发生脱质子作用,探讨了主客体之间的作用机理。并直接用于水相中无机醋酸盐的直接显色检测。     

The Squaramide versus Urea Contest for Anion Recognition

The interaction of a neutral squaramide‐based receptor, equipped with two 4‐nitrophenyl substituents ( R_sq ), with halides and oxoanions has been studied in MeCN. UV/Vis and ¹H NMR spectroscopy titration experiments clearly indicated the formation of 1:1 hydrogen bonding [ R_sq ???X]⁺ complexes with all the investigated anions. X‐ray diffraction studies on the chloride and bromide complex salts confirmed the 1:1 stoichiometry and indicated the establishment of bifurcated hydrogen‐bond interactions between the squaramide‐based receptor and the halide anion that involved both 1) amide N? H and 2) aryl proximate C? H fragments, for a total of four bonds. Probably due to the contribution of C? H fragments, complexes of R_sq with halides are 1 to 2 orders of magnitude more stable than the corresponding ones with the analogous urea‐based receptor that contains two 4‐nitrophenyl substituents ( R_ur ). In the case of oxoanions, R_sq forms complexes, the stability of which decreases with the decreasing basicity of the anion (H₂PO₄^?>NO₂^?≈HSO₄^?>NO₃^?), and is comparable to that of complexes of the urea‐based receptor R_ur . Such a behaviour is ascribed to the predominance of different contributions: electrostatic interaction for halides, acid‐to‐base ‘frozen’ proton transfer for oxoanions. Finally, with the strongly basic anions F^? and CH₃COO^?, R_sq first gives genuine hydrogen‐bond complexes of 1:1 stoichiometry; then, upon addition of a second anion equivalent, it undergoes deprotonation of one N? H fragment, with the simultaneous formation of the dianion hydrogen‐bond complexes, [HF₂]^? and [CH₃COOH???CH₃COO]^?, respectively. In the case of the urea‐based derivative R_ur , deprotonation takes place with fluoride but not with acetate. The apparently higher Brønsted acidity of R_sq with respect to R_ur reflects the capability of the squaramide receptor to delocalise the negative charge formed on N? H deprotonation over the cyclobutene‐1,2‐dione ring and the entire molecular framework.     

A dipodal thiourea-ionic liquid conjugate system for selective ratiometric detection of HSO4− ion in purely aqueous medium: Application to real sample analysis

A benzimidazolium based thiourea conjugate (IL) receptor has been designed, synthesized and characterized spectroscopically. The prepared receptor (IL) shows the sensitive and selective ratiometric sensing for HSO₄^? over the other anions as evident by UV–visible absorption and fluorescence spectroscopy. With the addition of HSO₄^? ion, the parent absorption band of IL in UV–visible absorption at 311 nm was shifted to 261 nm having an isosbestic point at 294 nm, which clearly indicates an interaction between HSO₄^? ion and the IL. Further, upon excitation at 310 nm, the fluorescence emission of IL at 455 nm was observed. Furthermore, the gradual addition of HSO₄^? ion results in a drastic decrease in emission at 455 nm and simultaneous appearance of a new emission band at 379 nm with isosbestic point at 430 nm was observed. The binding mechanism of HSO₄^? with IL was also explored with ¹H NMR titration, mass spectrometry and DFT calculations. These studies revealed the involvement of hydrogen bonding with –NH (thiourea) and –CH (benzimidazolium) functionalities towards the recognition of HSO₄^? ion. The association constant (K_a) and lowest detection limits for HSO₄^? were determined to be 5.437 × 10⁴ M^?1 and 5.0 nM, respectively. The real sample analysis by synthesized sensor probe for HSO₄^? was also performed which shows the practical applicability of the developed sensor system.     

Anion Binding‐Induced White Light Emission using a Water‐Tolerant Fluorescent Molecular Tweezer

A novel fluorescent molecular tweezer (FMT), built on the pyridine‐2,6‐bis‐carboxamide framework, has been developed that, in presence of a red emitter, gives rise to white light emission in response to the addition of H₂PO₄^? anions. The FMT incorporates two pyrene moieties as fluorescent reporter units and a strategically placed amine residue that imparts pH sensitivity to the fluorescence and offers additional electrostatic/hydrogen‐bonding interactions to the anions. As a result, this FMT selectively binds monoanionic tetrahedral oxyanions such as H₂PO₄^? and HSO₄^? that contain hydrogen bond donors and acceptors, and can sense their presence in aqueous acetonitrile through changes in fluorescence. Anion binding results in excimer formation by the pyrenes and a bluish‐green emission from the FMT. Both amide and amine residues of the FMT interact with these anions. The binding stoichiometry with H₂PO₄^? and HSO₄^? was found to be 1:1 and affinity of the FMT for these anions is of the order of 10⁴ m ^?1. The limit of detection for H₂PO₄^? was found to be 13 nm . Addition of a perylene monoimide‐based red emitter gives rise to panchromatic emission perceived as white light.     

Excited‐State Hydrogen Bonding Strengthening and Weakening with Intramolecular Charge Transfer in Resorufin‐Water Complexes: A TD‐DFT Study

The geometric structures, infrared spectra and hydrogen bond binding energies of the various hydrogen‐bonded Res^?‐water complexes in states S0 and S1 have been calculated using the density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT) methods, respectively. Based on the changes of the hydrogen bond lengths and binding energies as well as the spectral shifts of the vibrational mode of the hydroxyl groups, it is demonstrated that hydrogen bonds HB‐II, HB‐III and HB‐IV are strengthened while hydrogen bond HB‐I is weakened in the four singly hydrogen‐bonded Res^?‐Water complexes upon photoexcitation. When the four hydrogen bonds are formed simultaneously between one resorufin anion and four water molecules in the Res^?‐4Water complex, all the hydrogen bonds are weakened in both the ground and excited states compared with those in the corresponding singly hydrogen‐bonded Res^?‐Water complexes. Furthermore, in complex Res^?‐4Water, hydrogen bonds HB‐II and HB‐IV are strengthened while hydrogen bonds HB‐I and HB‐III are weakened after the electronic excitation. The hydrogen bond strengthening and weakening in the various hydrogen‐bonded Res^?‐water complexes should be due to the redistribution of the charges among the four heteroatoms (O_1‐3 and N₁) within the resorufin molecule upon the optical excitation.     

Synthesis and evaluation of neutral anion receptors based on acylhydrazide-appended calix[4]arenes

A new class of neutral receptors based upon acylhydrazide-appended calix[4]arenes was synthesised and evaluated for recognition of anions. Detailed NMR and single-crystal X-ray analyses of one of the synthesised compounds reveal that anion recognition in such derivatives is achieved through cooperative hydrogen bond interactions. The presence of three centred NH–O and two OH–O hydrogen bonds at the lower rim of the synthesised calixarene architecture apparently helps the molecular scaffold to retain cone conformation to enable deployment of intermolecular hydrogen bonds for selective recognition of HSO₄ ^? ion in preference to F^?, Cl^?, Br^?, I^?, ClO₄ ^?, AcO^? and PF₆ ^? ions.     

A Series of Amino Acid Functionalized Tripodal Hexaamide Anion Receptors: Ion‐Pair‐Assisted Capped‐Cleft Formation by a Pentafluorophenyl‐Functionalized Amide

A new series of tris(2‐aminoethyl)amine (tren)‐based L ‐alanine amino acid backboned tripodal hexaamide receptors (L1–L5) with various attached moieties based on electron‐withdrawing fluoro groups and lipophilicity have been synthesized and characterized. Detailed binding studies of L1–L5 with different anions, such as halides (F^?, Cl^?, Br^?, and I^?) and oxyanions (AcO^?, BzO^? (Bz=benzoyl), NO₃^?, H₂PO₄^?, and HSO₄^?), have been carried out by isothermal titration calorimetric (ITC) experiments in acetonitrile/dimethylsulfoxide (99.5:0.5 v/v) at 298 K. ITC titration experiments have clearly shown that receptors L1–L4 invariably form 1:1 complexes with Cl^?, AcO^?, BzO^?, and HSO₄^?, whereas L5 forms a 1:1 complex only with AcO^?. In the case of Br^?, I^?, and NO₃^?, no appreciable heat change is observed owing to weak interactions between these anions and receptors; this is further confirmed by ¹H NMR spectroscopy. The ITC binding studies of F^? and H₂PO₄^? do not fit well for a 1:1 binding model. Furthermore, ITC binding studies also revealed slightly higher selectivity of this series of receptors towards AcO^? over Cl^?, BzO^?, and HSO₄^?. Solid‐state structural evidence for the recognition of Cl^? by this new category of receptor was confirmed by single‐crystal X‐ray structural analysis of the complex of tetrabutylammonium chloride (TBACl) and L1. Single‐crystal X‐ray diffraction clearly showed that the pentafluorophenyl‐functionalized amide receptor (L1) encapsulated Cl^? in its cavity by hydrogen bonds from amides, and the cavity of L1 was capped with a TBA cation through hydrogen bonding and ion‐pair interactions to form a capped‐cleft orientation. To understand the role of the cationic counterpart in solution‐state Cl^? binding processes with this series of receptors (L1–L4), a detailed Cl^? binding study was carried out with three different tetraalkylammonium (Me₄N⁺, Et₄N⁺, and Bu₄N⁺) salts of Cl^?. The binding affinities of these receptors with different tetralkylammonium salts of Cl^? gave binding constants with the TBA cation in the following order: butyl>ethyl>methyl. This study further supports the role of the TBA countercation in ion‐pair recognition by this series of receptors.     

Electrocatalytic Hydrogen Production by a Nickel(II) Complex with a Phosphinopyridyl Ligand

A novel nickel(II) complex [Ni(L)₂Cl]Cl with a bidentate phosphinopyridyl ligand 6‐((diphenylphosphino)methyl)pyridin‐2‐amine (L) was synthesized as a metal‐complex catalyst for hydrogen production from protons. The ligand can stabilize a low Ni oxidation state and has an amine base as a proton transfer site. The X‐ray structure analysis revealed a distorted square‐pyramidal Ni^II complex with two bidentate L ligands in a trans arrangement in the equatorial plane and a chloride anion at the apex. Electrochemical measurements with the Ni^II complex in MeCN indicate a higher rate of hydrogen production under weak acid conditions using acetic acid as the proton source. The catalytic current increases with the stepwise addition of protons, and the turnover frequency is 8400 s^?1 in 0.1 m [NBu₄][ClO₄]/MeCN in the presence of acetic acid (290 equiv) at an overpotential of circa 590 mV.     

Reaction‐Based Colorimetric and Ratiometric Fluorescence Sensor for Detection of Cyanide in Aqueous Media

A stilbene‐based compound ( 1 ) has been prepared and was highly selective for the detection of cyanide anion in aqueous media even in the presence of other anions, such as F^?, Cl^?, Br^?, I^?, ClO₄^?, H₂PO₄^?, HSO₄^?, NO₃^?, and CH₃CO₂^?. A noticeable change in the color of the solution, along with a prominent fluorescence enhancement, was observed upon the addition of cyanide. The color change was observed upon the nucleophilic addition of the cyanide anion to the electron‐deficient cyanoacrylate group of 1 . The spectral changes induced by the reaction were analyzed by comparison with two model compounds, such as compound 2 with dimethyl substituents and compound 3 without a cyanoacrylate group. An intramolecular charge‐transfer (ICT) mechanism played a key role in the sensing properties, and the mechanism was supported by DFT/TDDFT calculations.     

Effect of Hydrogen Binding on Selective Recognition of Halide Anions

The interplay of molecular rigidity enforced by interior or exterior hydrogen bonding and affinity for binding halide anions is described to demonstrate the effect of intramolecular hydrogen bonding in anion recognition process. To this end pyridine‐2,6‐dicarboxamides 1 and 2 , and aromatic oligoamides 3 and 4 containing intramolecular hydrogen bonds were explored for their ability in associating with tetrabutylammonium halide (Cl^?, Br^?, and I^?). Binding constants in chloroform solution were calculated using nonlinear curve‐fitting method based on ¹H NMR titration experiments. The trimeric amide 3 , which adopts a crescent conformation as revealed by single‐crystal X‐ray diffraction analysis, strongly binds chloride anion with binding constant as high as 379 L·mol^?1. This is more than 6 times greater than the binding constant for the control receptor 2 with a backbone that is only partially rigidified. The comparative data provided supportive information for rationalizing the observed affinity difference in binding halide anions in terms of local preorganization effected by interior or exterior hydrogen bonding.     

On the Use of a Protic Ionic Liquid with a Novel Cation To Study Anion Basicity

The need for reliable means of ordering and quantifying the Lewis basicity of anions is discussed and the currently available methods are reviewed. Concluding that there is need for a simple impurity‐insensitive tool, we have sought, and here describe, a new method using NMR spectroscopy of a weak base, a substituted urea, 1,3‐dimethyl‐2‐imidazolidinone (DMI), as it is protonated by Brønsted acids of different strengths and characters. In all cases studied the product of protonation is a liquid (hence a protic ionic liquid). NMR spectroscopy detects changes in the electronic structure of the base upon interaction with the proton donors. As the proton‐donating ability, that is, acidity, increases, there is a smooth but distinct transition from a hydrogen‐bonded system (with no net proton transfer) to full ionicity. The liquid state of the samples and high concentration of nitrogen atoms, despite the very low natural abundance of its preferred NMR‐active isotope (¹⁵N), make possible the acquisition of ¹⁵N spectra in a relatively short time. These ¹⁵N, along with ¹³C, chemical shifts of the carbonyl atom, and their relative responses to protonation of the carbonyl oxygen, can be used as a means, sensitive to anion basicity and relatively insensitive to impurities, to sort anions in order of increasing hydrogen bond basicity. The order is found to be as follows: SbF₆^?<BF₄^?<NTf₂^?>ClO₄^?>FSO₃^?<TfO^?<HSO₄^?<Cl^?<MsO^?.