scholarly journals Extraction-Spectrophotometric Studies on the Ion-Pairing Between Some 2,3,5-Substituted Monotetrazolium Cations and Anions Deriving from 4-(2-Thiazolylazo)resorcinol or 4-(2-Pyridylazo)resorcinol

2009 ◽  
Vol 5 (2) ◽  
pp. 641-651 ◽  
Author(s):  
Kiril Blazhev Gavazov ◽  
Galya K. Toncheva

The ion-pairing between some 2,3,5-substituted monotetrazolium cations (T+) and anions deriving from 4-(2-pyridylazo)resorcinol (PAR) or 4-(2-thiazolylazo)resorcinol (TAR) was studied by water-chloroform extraction and spectrophotometry. The following tetrazolium salts (TS) were used as a source of T+: i) 2,3,5-triphenyl-2H-tetrazolium chloride (TTC); ii) 3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (MTT); iii) 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet, TV); and iv) 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (INT). The spectral characteristics of the extracted species were established at different pH and TS concentration. The composition and stability of the ion-pairs were determined at pH 9, where the extraction of neutral PAR (H2PAR) and TAR (H2TAR) species was negligible. The results showed that the ion-pairs can be expressed with the following formulae (T+)(HTAR–) (where T+ = TT+, MTT+, TV+ or INT+), (T+)(HPAR–) (where T+ = TT+, MTT+ or TV+) and [(INT+)(HPAR–)]2. Relationships involving the molecular masses of the ion-pairs (MIP) or T+ (MT+) and the values of the constants of association (b) or conditional molar absorptivities (e’) were examined, namely Log b = f(Log MIP) and e’ = f(Log MT+). Some practical aspects concerning the investigation of metal complexes with TS-PAR/TS-TAR were discussed.

2020 ◽  
Author(s):  
James Sterling ◽  
Wenjuan Jiang ◽  
Wesley M. Botello-Smith ◽  
Yun L. Luo

Molecular dynamics simulations of hyaluronic acid and heparin brushes are presented that show important effects of ion-pairing, water dielectric decrease, and co-ion exclusion. Results show equilibria with electroneutrality attained through screening and pairing of brush anionic charges by cations. Most surprising is the reversal of the Donnan potential that would be expected based on electrostatic Boltzmann partitioning alone. Water dielectric decrement within the brush domain is also associated with Born hydration-driven cation exclusion from the brush. We observe that the primary partition energy attracting cations to attain brush electroneutrality is the ion-pairing or salt-bridge energy associated with cation-sulfate and cation-carboxylate solvent-separated and contact ion pairs. Potassium and sodium pairing to glycosaminoglycan carboxylates and sulfates consistently show similar abundance of contact-pairing and solvent-separated pairing. In these crowded macromolecular brushes, ion-pairing, Born-hydration, and electrostatic potential energies all contribute to attain electroneutrality and should therefore contribute in mean-field models to accurately represent brush electrostatics.


2021 ◽  
Vol 57 (35) ◽  
pp. 4287-4290
Author(s):  
Ryohei Yamakado ◽  
Issei Kitamura ◽  
Mitsuo Hara ◽  
Shusaku Nagano ◽  
Takahiro Seki ◽  
...  

Large mass transport driven by the difference in the photoisomerization-induced surface tension was demonstrated in ion pairs, enabling fluorescence patterning using a trace amount of photoisomerized anions in complexation with a π-electronic system.


2021 ◽  
Vol 23 (12) ◽  
pp. 7480-7494
Author(s):  
Sarah Karbalaei Khani ◽  
Bastian Geissler ◽  
Elric Engelage ◽  
Patrick Nuernberger ◽  
Christof Hättig

Spectroscopic signatures of ion-pairing are identified by variation of counterion and substitution and comparison with theory.


2016 ◽  
Vol 13 (1) ◽  
pp. 76 ◽  
Author(s):  
Herman P. van Leeuwen ◽  
Raewyn M. Town

Environmental context Humic acids are negatively charged soft nanoparticles that play a governing role in the speciation of many ionic and molecular compounds in the environment. The charge density in the humic acid nanoparticle can be very high and the binding of divalent cations such as Ca2+ appears to go far beyond traditional ion pairing or Poisson–Boltzmann electrostatics. A two-state approach, combining counterion condensation in the intraparticulate double layer and classical Donnan partitioning in the bulk of the particle, provides a satisfactory description of the physicochemical speciation. Abstract Experimental data for divalent counterion binding by soil humic acid nanoparticles are set against ion distributions as ensuing from continuous Poisson–Boltzmann electrostatics and a two-state condensation approach. The results demonstrate that Poisson–Boltzmann massively underestimates the extent of binding of Ca2+ by humic acid, and that electric condensation of these counterions within the soft nanoparticulate body must be involved. The measured stability of the Ca2+–humic acid associate is also much greater than that predicted for ion pairing between single Ca2+ ions and monovalent negative humic acid sites, which also points to extensive electrostatic cooperativity within the humic acid particle. At sufficiently high pH, the charge density inside the humic acid entity may indeed become so high that the bulk particle attains a very high and practically flat potential profile throughout. At this limit, all the intraparticulate Ca2+ is at approximately the same electrostatic potential and the status of individual ion pairs has become immaterial. A two-state model, combining counterion condensation in the charged intraparticulate part of the double layer at the particle–medium interface and Donnan partitioning in the uncharged bulk of the humic acid particle, seems to lead the way to adequate modelling of the divalent counterion binding for various particle sizes and different ionic strengths.


1990 ◽  
Vol 45 (8) ◽  
pp. 1197-1204 ◽  
Author(s):  
H. Bock ◽  
P. Hänel ◽  
H.-F. Herrmann

The radical anion of dimesityltetraketone (ERed, I = -0.40 V) is easily generated in THF by potassium mirror/[2.2.2]-cryptand reduction. Its contact ion pairs with Na⊕, Cs⊕ and Ba⊕⊕ counter cations, prepared in THF solution by single electron transfer from the respective metals, are characterized by their ESR/ENDOR spectra, which exhibit temperature-dependent metal couplings of aNa⊕ = 0.061 mT (190 K), aCs⊕ = 0.021 mT (190 K), and aBa⊕⊕ = 0.145 mT (295 K).


2020 ◽  
Vol 5 (4) ◽  
pp. 757-771
Author(s):  
Yohei Haketa ◽  
Kazuki Urakawa ◽  
Hiromitsu Maeda

The prologue and progress of π-electronic ion-pairing assemblies, including synthesis of π-electronic ions, preparation of ion pairs, fabrication of assemblies as crystals, gels and liquid crystals and their characteristic properties, are summarized.


2007 ◽  
Vol 5 (1) ◽  
pp. 257-270 ◽  
Author(s):  
Kiril Gavazov ◽  
Vanya Lekova ◽  
Atanas Dimitrov ◽  
Georgi Patronov

AbstractThe formation and extraction of ion-associate complexes between the vanadium(V)-4-(2-thiazolylazo)resorcinol (TAR) anionic chelate and the cations of some mono-and ditetrazolium salts {3-(4,5-dimethyl-2-thiazol)-2,5-diphenyl-2H-tetrazolium bromide (Thiazolyl blue, MTT), 3-(2-naphtyl)-2,5-diphenyl-2H-tetrazolium chloride (Tetrazolium violet), 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride (Iodonitrotetrazolium chloride), 3,3′-[3,3′-dimetoxy(1,1′-biphenyl)-4,4′-diyl]-bis[2,5-diphenyl-2H-tetrazolium] chloride (Tetrazolium blue chloride) and 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium chloride] (Nitro blue tetrazolium chloride)} have been studied. The optimum extraction conditions have been found. The composition of the V-TAR-monotetrazolium and V-TAR-ditetrazolium complexes extracted into chloroform has been determined to be 1:2:3 and 2:4:3 respectively. The extraction, distribution and association constants, and the recovery factors have been calculated. The relationship between the molecular weight of tetrazolium cations, and the association constants of their complexes has been discussed. The special behavior of the tetrazolium cations, containing-NO2 groups has been noticed. The effects of foreign ions and reagents on the extraction of vanadium with TAR and the best tetrazolium salt-MTT have been studied. A sensitive, selective, simple and fast method for the determination of vanadium has been developed.


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