Hydrogen Sulfate Ion Research Articles

Does the compound hexaaqua-zinc(ii)bis(hydrogensulfate)dihydrate, [Zn(H2O)6](HSO4·H2O)2, really exist?

A careful examination of the crystal structure of the hydrogensulfate compound [Zn(H2O)6](HSO4·H2O)2 reported in this journal shows that the sample used for X-ray diffraction was almost certainly the Tutton salt [Zn(H2O)6](SO4·NH4)2, isoelectronic with the former elusive compound (F000 = 416, P21/c space group). Indeed, any chemistry involving ammonium and sulfate moieties in an aqueous medium containing a transition metal cation should afford the corresponding Tutton salt as a by-product. We redetermined the structure of [Zn(H2O)6](SO4·NH4)2, on the basis of high-resolution X-ray data (d = 0.47 Å), with the purpose of illustrating that at such resolution, difference Fourier maps may be used to unambiguously differentiate between a sulfate and a hydrogensulfate ion. On the other hand, regardless of the data resolution, geometrical considerations may be enough to avoid misassignment of such small ions in crystal structures, providing that some knowledge about the average shape of these ions is available from curated crystallographic databases.

Visible Light Controlled Aggregation of a Spiropyran‐HSO4− Complex as a Strategy for Reversible Detection in Water

AbstractA merocyanine salt form of a substituted spiropyran was synthesized and evaluated for stimuli‐responsive properties. The HSO4− induced H‐aggregation of the merocyanine salt was used as a strategy for detection in pure water. The anion induced aggregation was controlled by light, which converted the open merocyanine form into the closed spiropyran form. The formation of the closed form released the hydrogen sulfate ion. The DLS and TEM analyses were used to investigate the aggregation and disaggregation of the merocyanine salt form of a spiropyran. Therefore, the study establishes the first example of reversible, highly selective and nanomolar level response towards HSO4− ion in water.

Optical sensing of hydrogen sulphate using rhodamine 6G hydrazide from aqueous medium

This communication reports the application of rhodamine 6G hydrazide (L) for the selective colorimetric and turn-on fluorescent sensing of hydrogen sulphate ions from aqueous medium. The ring opening of the colourless spirocyclic form of L was selectively triggered in the presence of HSO4− among the other tested anions (F−, Cl−, Br−, I−, AcO−, H2PO4−, NO3−, ClO4−, CN−, HO−, AsO33− and SO42−), which gives rise to a pink colour and strong fluorescence in the visible region. Sensor L showed a detection limit down to micromolar range without any interference from the other tested competitive anions. Sensor L was applied for the construction of two inputs (HO– and HSO4−) INHIBIT type molecular logic gate and naked-eye detection of HSO4− using test paper strips.

1-Butyl-3-methylimidazolium hydrogen sulfate catalyzed in-situ transesterification of Nannochloropsis to fatty acid methyl esters

1-Butyl-3-methylimidazolium hydrogen sulfate ([Bmim][HSO4]) is used as a solvent and an acid catalyst for in-situ extractive transesterification of wet Nannochloropsis with methanol. The reaction is supposed to be a five-step process: (1) wet algae cell wall dissolves in ionic liquid at reaction temperatures; (2) hydrogen ions and sulfate ions release from the ionization of HSO4−. The hydrogen ions (H+) act as catalysts for accelerating the reactive extraction of triglyceride from wet Nannochloropsis; (3) hydrogen ions and methanol molecules transfer from bulk to active site of cells without passing through cell wall that is dissolved by ionic liquid; (4) in-situ transesterification of lipid (mainly triglycerides) with methanol; and (5) products transfer from inside of algae cells to outside of cells. The crude biodiesel yield of [Bmim][HSO4] catalyzed in-situ transesterification is about 95.28% at reaction temperature of 200°C, reaction time of 30min, mass ratio of [Bmim][HSO4] to wet Nannochloropsis of 0.9:1, and a mass ratio of methanol to wet algae of 3:1. It decreases to 81.23% after [Bmim][HSO4] is recycled for 4 times, which indicates that [Bmim][HSO4] catalyzed in-situ transesterification is an economic approach for biodiesel production from wet algae.

A Molecular Lock with Hydrogen Sulfate as “Key” and Fluoride as “Hand”: Computing Based Insights on the Functioning Mechanism

AbstractThe present work demonstrates a new fully regenerative, molecular machine‐like “ON‐OFF‐ON” chemosensor based on a β‐carboline molecule “OFF‐ON‐OFF” cycle. It behaves as a molecular lock that requires a hydrogen sulfate (HSO4−) ion as “key” to open the lock and a fluoride (F−) ion as “hand” that removes the key from the lock to close the lock. The reversibility and reusability of sensor for the detection of hydrogen sulfate and fluoride ions were tested for six cycles. Experimental and computational studies reveal that the proton transfer process from hydrogen sulfate (HSO4−) ion to the pyridinic nitrogen atom of norharmane leading to the formation of a hydrogen bonded ion pair (HBIP) provides the optical changes in the visible region that are advantageous for real time and on‐site application.

Hydrogen sulfate ion sensing in aqueous media based on a fused pyrimido benzothiazole derivative

The receptor 3-cyano-4-imino-2-methylthio-4H-pyrimido[2,1-b][1,3]benzothiazole (SVK-1) was employed for the selective sensing of HSO4−ions in aqueous media.

Crystal structure of tris-(piperidinium) hydrogen sulfate sulfate.

In the title molecular salt, 3C5H12N(+)·HSO4 (-)·SO4 (2-), each cation adopts a chair conformation. In the crystal, the hydrogen sulfate ion is connected to the sulfate ion by a strong O-H⋯O hydrogen bond. The packing also features a number of N-H⋯O hydrogen bonds, which lead to a three-dimensional network structure. The hydrogen sulfate anion accepts four hydrogen bonds from two cations, whereas the sulfate ion, as an acceptor, binds to five separate piperidinium cations, forming seven hydrogen bonds.

Synthesis and UV/Vis analysis of amino acid-derived bisurea-type receptors involving anion complexation

AbstractSixteen new bisurea compounds incorporating versatile proteinogenic amino acids as well as nipecotic acid have been synthesizedviaaddition reaction to aryl diisocyanates. The products were analytically characterized and their ability for anion recognition was studied by UV/Vis spectroscopy. In the presence of fluoride, acetate or dihydrogenphosphate ions, hyperchromic and bathochromic peak shifts were determined. By way of contrast, bromide, iodide, or hydrogensulfate ions cause no significant change of absorbance. The special effect of heterocyclic derivatives was explained by molecular modeling calculations. In addition, the crystal structure of the byproduct dimethylN,N′-(1,4-phenylene)dicarbamate is discussed.

A bio-attuned ratiometric hydrogen sulfate ion selective receptor in aqueous solvent: structural proof of the H-bonded adduct

A new cell permeable quinazoline based receptor (1) behaves as a highly selective chemosensor for HSO4− ions at nanomolar concentration in aqueous medium by formation of the adduct [LHSO4]−LH+·3H2O confirmed by single crystal X-ray crystallography.

Properties of chemically generated π-radical cations and molecules of (meso-phenyl-β-octaethylporphyrinato)rhenium(V) with axial molecular oxygen

The state of existence and reactions of stable rhenium(V) complexes with β-octaethylporphin (O=Re(OPh)OEP, O=Re(Cl)OEP) and its meso-diphenyl-substituted derivatives (O=Re(Cl)5,15DPOEP) in concentrated H2SO4 at 318–348 K were studied. It was found that O=Re(Cl)5,15DPOEP undergoes slow single-electron oxidation at the aromatic ligand to give π-radical cation. The oxidation is accompanied by replacement of the axial Cl− ligand by the hydrogen sulfate ion present in excess. Full kinetic description of the intricate oxidation reaction of the complex involving atmospheric oxygen was obtained and parameters of simple reactions that constitute the intricate process were determined. In the case of O=Re(Cl)OEP and O=Re(OPh)OEP, the reaction stops after the formation of the cationic complex with axially coordinated oxygen and outer-sphere chloride ion O=Re(O2)OEP+ Cl−. The effect of the nature of axial and macrocyclic ligands in rhenium(V) porphyrins on the processes in sulfuric acid solutions of these compounds was established.

Investigation of water–rock interactions in Cambrian black shale via a flow-through experiment

This paper summarizes the results of a flow-through experiment of our own design intended to investigate the water–rock interactions between pyrite embedded in black shale and dissolved oxygen in pore water. Deionized water in equilibrium with 3atm of PN2 or PO2 was flowed through a cylindrical rock specimen at 25°C. The electrical conductivity (EC) and pH values of the experimental outflow solutions were continuously monitored. First, original pore water was expelled by N2-saturated water followed by O2-saturated water. Concentrations of major ion species were determined for solutions periodically withdrawn from the experimental system. The changes in these components over time indicated that 1. The chemical composition of the original pore water in the black shale was rich in hydrogen ions, sulfate ions and iron species and that 2. Two major reactions, namely, ion exchange and pyrite oxidation, occurred during the water flow. The oxidation of pyrite in black shale was controlled by the concentration of dissolved oxygen asFeS2+7/2O2(aq)+H2O→Fe2++2SO42-+2H+,where the rate law for the reaction at pH=4.2–5.6 and T=25°C was determined to be Rsp=10−8.42±0.06 [O2]0.5 (molm−2s−1). This result is consistent with the reaction rate of pyrite grains with dissolved oxygen reported by previous researchers. Hydraulic conductivity decreased by approximately 12.5% during the nitrogen-inflow stage and by 69% during the oxygen-inflow stage. This change can be attributed to the oxidizing reaction within the rock and to the probable clogging of fine weathering products in the pore space. The geochemical modeling of the experimental outflowing water and seepage samples from the field using the PHREEQC program suggested that pore water develops into an acidic solution rich in iron and sulfate due to long-term pyrite oxidation and evaporation.

A fluorescent chemosensor for sequential recognition of gallium and hydrogen sulfate ions based on a new phenylthiazole derivative

A new highly selective turn-on fluorescent chemosensor based on 2′-hydroxyphenylthiazole for the detection of gallium and hydrogen sulfate ions in acetonitrile was synthesized and characterized. The mechanism of fluorescence was based on the inhibition of excited state intramolecular proton transfer (ESIPT). The sensor demonstrated high selectivity for gallium as compared to aluminum and other cations and allowed sequential detection of hydrogen sulfate.

Recovery of Nickel(II) Ions from Sulphate/Chloride Solutions Using Hydrophobic Pyridylketoximes

In this study, the extraction of nickel(II) ions from sulphate and sulphate/chloride solutions with 2-, 3-, and 4-pyridylketoximes was investigated. The effect of different variables influencing the extraction of nickel(II) ions such as the extractant structure and the concentration of hydrogen ion, sulphate, and chloride ions have been studied. The shaking time and temperature also influenced metal ion removal. It was found that the hydrophobic 2-pyridylketoximes are the most effective extractants for nickel ions from sulphate/chloride solutions. The discussion also includes the mechanism of nickel(II) complexation by the hydrophobic pyridylketoximes and the speciation of nickel(II) in the presence of chloride and sulphate ions.

Development of a cell permeable ratiometric chemosensor and biomarker for hydrogen sulphate ions in aqueous solution

A newly designed benzimidazol-based water soluble ratiometric chemosensor selective for HSO4− ions behaves as an efficient biomarker for the detection of the distribution of HSO4− ions in living cells in HEPES buffer (1 mM; water : ethanol (v/v), 98 : 2).

A turn‐on indole‐based sensor for hydrogen sulfate ion

A simple indole-based receptor 1 was prepared by a simple Schiff-base reaction of 1H-indole-3-carbaldehyde with ethane 1,2-diamine and its fluoroionophoric properties toward anions were investigated. Indole-based receptor 1 acts as a selective turn-on fluorescent sensor for HSO4(-) in methanol among a series of tested anions. Fluorescence spectroscopy, ultraviolet and nuclear magnetic resonance imaging support that the HSO4(-) indeed interacted with imine nitrogen and the proton of nitrogen in indole ring.

Manganese Ions Complexation Processes with Organic and Inorganic Compounds and their Migration in a Low-flowing Water Body Ecosystem

Processes of metal ions complexation in a water system containing hydrogen carbonate ions and sulphate ions, as well as dead off supreme aquatic vegetation organic matter and organic compounds of protein origin have been considered. Complexation processes’ interconnection with manganese ions migration in a low-flowing water body has been justified.

A polymeric film probe with a turn-on fluorescence response to hydrogen sulfate ions in aqueous media.

A new kind of hydrophilic copolymer poly(HEMA-co-VNP) was designed and synthesized by the radical copolymerization of 2-hydroxyethylmethacrylate (HEMA) and 2-{[2-(4-vinylbenzyloxy)naphthalen-1-yl]methyleneamino}-(S)-2-phenylethanol (VNP). The desired copolymer showed a highly selective red-shifted emission and a unique chiroptical response upon HSO4 - binding in organic solution. UV-vis and 1H NMR spectroscopic studies revealed that the hydrogen bonding between the imine moiety in the VNP repeating units and HSO4 - is crucial for the high selectivity of the receptor to this anion. As expected, the incorporation of HEMA into the polymer matrix endowed the copolymer excellent hydrophilicity, flexibility and good film-forming properties. Thus, high-quality film sensors could be easily fabricated on quartz plates through spin-casting techniques. The resultant polymeric films can recognize HSO4 - ions among a series of common anions in aqueous solution with high selectivity and sensitivity. The promising new film probe for HSO4 - has distinct characteristics such as a rapid response, enough stability in an aqueous media and practicality.

A hydrogen sulfate salt of chlordiazepoxide

Crystals of the hydrogen sulfate salt of chlordiazepoxide (systematic name: 7-chloro-N-methyl-5-phenyl-2,3-dihydro-1H-1,4-benzodiazepin-2-iminium 4-oxide hydrogen sulfate), C16H15ClN3O+·HSO4 −, were obtained from a solution of chlordiazepoxide and sulfuric acid in methanol. The structure features chlordiazepoxide mol­ecules that are protonated at the imine N atom. The seven-membered ring adopts a boat conformation with the CH2 group as the prow and the two aryl C atoms as the stern. The dihedral angle between the benzene rings is 72.41 (6)°. In the crystal, the HSO4 − anion acts as a bridging group between two chlordiazepoxide cations. The H atom of the protonated imino N forms an N—H⋯O hydrogen bond with a hydrogen sulfate ion. The anion in turn forms two hydrogen bonds, O—H⋯O with the anion as donor and N—H⋯O with the anion as acceptor, to generate an R 2 2(10) loop. Each HSO4 − anion connects two chlordiazepoxide moieties of the same chirality.

Tris(cis-2-hydroxycyclohexane-1,3,5-triaminium) hydrogen sulfate octachloride dihydrate

The 2-hy­droxy­cyclo­hexane-1,3,5-triaminium (= H3 L 3+) cation of the title compound, 3C6H18N3O3+·8Cl−·HSO4 −·2H2O, exhibits a cyclo­hexane chair with three equatorial ammonium groups and one axial hy­droxy group in an all-cis configuration. The hydrogen sulfate anion and two water mol­ecules lie on or in proximity to a threefold axis and are disordered. The crystal structure features N—H⋯Cl and O—H⋯Cl hydrogen bonds. Three C 3-symmetric motifs can be identified in the structure: (i) Two chloride ions (on the C 3-axis) together with three H3 L 3+ cations constitute an [(H3 L)3Cl2]7+ cage. (ii) The lipophilic C6H6-sides of three H3 L 3+ cations, which are oriented directly towards the C 3-axis, generate a lipophilic void. The void is filled with the disordered water mol­ecules and with the disordered part of the hydrogen sulfate ion. The hydrogen atoms of these disordered moieties were not located. (iii) Three H3 L 3+ cations together with one HSO4 − and three Cl− counter-ions form an [(HSO4)(H3 L)3Cl3]5+ cage. Looking along the C 3-axis, these three motifs are arranged in the order (cage 1)⋯(lipophilic void)⋯(cage 2). The crystal studied was found to be a racemic twin.

A fluorescence enhancement-based sensor for hydrogen sulfate ion

Sugar-aza-crown ether-based cavitand 1 can act as a selective turn-on fluorescence sensor for hydrogen sulfate ion in methanol among a series of tested anions. Spectroscopic studies, particularly NMR spectroscopy, revealed that the C-H hydrogen bonding between 1,2,3-triazole ring of cavitand 1 and hydrogen sulfate ion is crucial for the high selectivity of the receptor for hydrogen sulfate.