Electrospray ionization mass spectrometric solvate cluster and multiply charged ions: a stochastic dynamic approach to 3D structural analysis

Abstract

The data analyzed in this paper are on quantitative and 3D structural determination of ionic ensembles and multiply charged solvates ions of type [(Cl)(H 2 O) x (H 3 O) y (CH 3 CN) z ] + , [(Cl)(O 2) x (CH 3 OH) y (NH 4) z ] + , [(O 2) x (H 2 O)(H 3 O)(CH 3 CN)] + n and [(Cl) (H 2 O) 2 (H 3 O)(CH 3 CHN 2)] + observable under electrospray ionization conditions in presence of Zn II-ion containing metalorganics, where x = y = z = 1-3 are the number of molecules, respectively, ions participating into each of the interacting ensemble, while "n" denotes the number of interacting ensembles forming the more complex ionic clusters. The major theoretical problem we have to deal with is the applicability of our more recently developed stochastic dynamic concept and formulas connecting among the mass spectrometric variable intensity, the so-called stochastic dynamic diffusion parameters (D SD), the temperature (T) and the analyte concentration in solution to such challenging molecular/ionic systems from the perspective of molecular structure. The D SD parameters of analyte ions correlate linearly with the socalled quantum chemical diffusion parameters (D QC) according to the Arrhenius's theory. The work has demonstrated persuasively that these equations are capable of providing reliable analytical information about so complex ensembles of interacting species. It shows their significant advantages as analytical approaches, amongst other rival concepts, to quantify the mass spectrometric outcome intensity highly accurately, selectively, precisely and sensitively. The thermodynamics parameters of common reactions of the following ionic species observable under electrospray ionization experimental conditions of some tetrachlrozinc(II) complex ions of metal-organics are examined. These are the ions [(Cl) (H 2 O)(H 3 O) 2 (CH 3 CN) 3 ] + (m/z 214/216), [(Cl)(H 2 O)(H 3 O) 2 (CH 3 CN) 2 ] + (m/z 173/175), [(Cl)(H 2 O) 2 (H 3 O) 2 (CH 3 CN)] + (m/z 150/152), [(Cl)(H 2 O)(H 3 O) 2 (CH 3 CHNH] + (m/z 134/136,) [(Cl)(H 2 O) 2 (H 3 O)(CH 3 CHNH 2 ] + , [(Cl)(H 2 O)(H 3 O) 2 (CH 3 CN] + (m/z 132/134,) [(Cl) (H 2 O) 2 (H 3 O) 2 (CH 3 CN] + (m/z 183/185), [(CH 3 OH)(H 2 O) 5 (NH 4)(CH 3 CN) 3 ] + 3 (m/z 263,) and [(CH 3 OH)(H 2 O)(H 3 O)(CH 3 CN)] + 31 (m/z 110,) respectively.

Recent Advances in Metal–Organic Frameworks for the Surface Modification of the Zinc Metal Anode: A Review

“…With a 4.2 mg cm −2 MnO 2 mass loading on the cathode, the MOF-coated Zn anode exhibited the specific capacity of 192.4 mAh g −1 at the 20th cycle, and a capacity retention of 94.4% after 180 cycles at 500 mA g −1 (Figure 2d). Due to the strong solute-solvent interactions, Zn 2+ exist in the form of complex ions in the electrolyte [59] and undergo a desolvation process before obtaining electrons, which reduces the reaction kinetics and induces side reactions. With narrower channels than solvated metal ions, the Zn MOF layer can effectively promote the solvated metal ions to remove or drop off parts of their sheath solvents, and consequently lead to desolvated electrolytes as host sieves with subnanometer-level sieving abilities (Figure 2b), which seems to be an impossible situation, even in the saturated ZnSO 4 solutions (Figure 2a) [60].…”