Formation and stability of the 4-methoxyphenonium ion in aqueous solution.
Ontology highlight
ABSTRACT:
SUBMITTER: Tsuji Y
PROVIDER: S-EPMC3225690 | biostudies-literature | 2011 Dec
REPOSITORIES: biostudies-literature
Publications
Formation and stability of the 4-methoxyphenonium ion in aqueous solution.
Tsuji Yutaka Y Hara Daisuke D Hagimoto Rui R Richard John P JP
The Journal of organic chemistry 20111103 23
The reaction of 2-methoxyphenylethyl tosylate (MeO-1-Ts) is first-order in [N(3)(-)]. A carbon-13 NMR analysis of the products of the reactions of MeO-1-[α-(13)C]Ts shows the formation of MeO-1-[β-(13)C]OH and MeO-1-[β-(13)C]N(3) from the trapping of a symmetrical 4-methoxyphenonium ion reaction intermediate 2(+). An analysis of the rate and product data provides a value of k(az)/k(s) = 83 M(-1) for partitioning of 2(+) between addition of azide ion and solvent. These data set a limit for the li ...[more]
Similar Datasets
Project description:Aqueous solutions of Lu3+- perchlorate, triflate and chloride were measured by Raman spectroscopy. A weak, isotropic mode at 396 cm-1 (full width at half height (fwhh) at 50 cm-1) was observed in perchlorate and triflate solutions. This mode was assigned to the totally symmetric stretching mode of [Lu(OH?)?]3+, ??LuO?. In Lu(ClO?)? solutions in heavy water, the ??LuO? symmetric stretch of [Lu(OD?)?]3+ appears at 376.5 cm-1. The shift confirms the theoretical isotopic effect of this mode. In the anisotropic scattering of aqueous Lu(ClO?)?, five bands of very low intensity were observed at 113 cm-1, 161.6 cm-1, 231 cm-1, 261.3 cm-1 and 344 cm-1. In LuCl? (aq) solutions measured over a concentration range from 0.105?3.199 mol·L-1 a 1:1 chloro-complex was detected. Its equilibrium concentration, however, disappeared rapidly with dilution and vanished at a concentration < 0.5 mol·L-1. Quantitative Raman spectroscopy allowed the detection of the fractions of [Lu(OH?)?]3+, the fully hydrated species and the mono-chloro complex, [Lu(OH?)?Cl]2+. In a ternary LuCl?/HCl solution, a mixtrure of chloro-complex species of the type [Lu(OH?)8-nCln]+3-n (n = 1 and 2) were detected. DFT geometry optimization and frequency calculations are reported for Lu3+- water cluster in vacuo and with a polarizable dielectric continuum (PC) model including the bulk solvent implicitly. The bond distance and angle for [Lu(OH?)?]3+ within the PC are in good agreement with data from structural experiments. The DFT frequencies for the Lu-O modes of [Lu(OH?)?]3+ and its deuterated analog [Lu(OD?)?]3+ in a PC are in fair agreement with the experimental ones. The calculated hydration enthalpy of Lu3+ (aq) is slightly lower than the experimental value.
| S-EPMC6321123 | biostudies-literature
Project description:Since the isolation of the first cytokinin almost 60 yr ago, cytokinins have become critically important for ornamental and agricultural crops in plant tissue culture. Despite the extensive research on this class of compounds, little information is available on the chemical stability of cytokinins in solution or following an autoclave cycle with Murashige and Skoog (MS) basal medium. This work describes the stability in aqueous solutions of five widely used adenine-based cytokinins: trans-zeatin (tZ), 6-(?,?-dimethylallylamino) purine (2iP), kinetin, benzyladenine (BA), and m-topolin. High pressure liquid chromatography (HPLC) and electrospray ionization-mass spectrometry (ESI-MS) were used to quantify and identify their degradation. BA, kinetin, 2iP, and m-topolin were stable at 1.0 mg mL-1 in 0.05 N KOH, with no statistically significant concentration changes (p?>?0.05) after 90 d of storage at temperatures of -20°C, 2-6°C, or 25°C. The cytokinin tZ was used as a model compound to evaluate stability under alkaline and acid conditions as well as after repeated freeze-thaw cycles. Trans-zeatin retained >90% of the initial concentration of 1.0 mg mL-1 when dissolved in 0.01 N KOH and stored at -20°C and 2-6°C for 90 d, with only the 2-6°C temperature treatment showing a statistical significant concentration change (p?=?0.03). The 1.0 mg mL-1 tZ solution in 0.01 N KOH was stable through six repeated freeze-thaw cycles over 90 d without any significant change in concentration compared to the initial freeze-thaw. Yet, tZ showed highly significant concentration changes when dissolved at 50 mg mL-1 and 0.5 N KOH. All of these adenine-based cytokinins showed exceptional stability following an autoclave cycle at 121°C, 110 kPa for 30 min when in solutions of 1.0 mg mL-1 in 0.05 N KOH, with no significant degradation detected. Trans-zeatin was also found to be stable after one autoclave cycle with 1× MS-basal salts.
| S-EPMC4759223 | biostudies-literature
Project description:Energy and environmental pollution have become the two major problems in today's society. The development of green energy storage devices with good safety, high reliability, high energy density and low cost are urgently demanded. Here we report on a lithium ion battery using an aqueous electrolyte solution. It is built up by using graphite coated with gel polymer membrane and LISICON as the negative electrode, and LiFePO4 in aqueous solution as the positive electrode. Its average discharge voltage is up to 3.1?V and energy density based on the two electrode materials is 258?Wh kg(-1). It will be a promising energy storage system with good safety and efficient cooling effects.
| S-EPMC4916472 | biostudies-literature
Project description:The lead(II) complexes formed with the multidentate chelator L-cysteine (H2Cys) in an alkaline aqueous solution were studied using (207)Pb, (13)C, and (1)H NMR, Pb LIII-edge X-ray absorption, and UV-vis spectroscopic techniques, complemented by electrospray ion mass spectrometry (ESI-MS). The H2Cys/Pb(II) mole ratios were varied from 2.1 to 10.0 for two sets of solutions with CPb(II) = 0.01 and 0.1 M, respectively, prepared at pH values (9.1-10.4) for which precipitates of lead(II) cysteine dissolved. At low H2Cys/Pb(II) mole ratios (2.1-3.0), a mixture of the dithiolate [Pb(S,N-Cys)2](2-) and [Pb(S,N,O-Cys)(S-HCys)](-) complexes with average Pb-(N/O) and Pb-S distances of 2.42 ± 0.04 and 2.64 ± 0.04 Å, respectively, was found to dominate. At high concentration of free cysteinate (>0.7 M), a significant amount converts to the trithiolate [Pb(S,N-Cys)(S-HCys)2](2-), including a minor amount of a PbS3-coordinated [Pb(S-HCys)3](-) complex. The coordination mode was evaluated by fitting linear combinations of EXAFS oscillations to the experimental spectra and by examining the (207)Pb NMR signals in the chemical shift range δPb = 2006-2507 ppm, which became increasingly deshielded with increasing free cysteinate concentration. One-pulse magic-angle-spinning (MAS) (207)Pb NMR spectra of crystalline Pb(aet)2 (Haet = 2-aminoethanethiol or cysteamine) with PbS2N2 coordination were measured for comparison (δiso = 2105 ppm). The UV-vis spectra displayed absorption maxima at 298-300 nm (S(-) → Pb(II) charge transfer) for the dithiolate PbS2N(N/O) species; with increasing ligand excess, a shoulder appeared at ∼330 nm for the trithiolate PbS3N and PbS3 (minor) complexes. The results provide spectroscopic fingerprints for structural models for lead(II) coordination modes to proteins and enzymes.
| S-EPMC4370366 | biostudies-literature
Project description:The conformation and structure of methyl cellulose (MC) ether samples dissolved in pure water under dilute conditions were carefully reconsidered based on the results obtained using small-to-wide-angle neutron scattering (S-WANS), static light scattering (SLS), dynamic light scattering (DLS), and viscometric techniques. The examined MC samples possessed an average degree of substitution by methyl groups per glucose unit of ca 1.8 and weight average molar masses (M w), ranging from 23 to 790 kg mol-1. S-WANS experiments clearly demonstrated that the samples possess highly elongated rigid rodlike local structures in deuterium oxide solutions with weak periodicities of ca 0.4 and 1.0 nm on a length scale, which correspond to the average intermolecular distance between molecular chain portions facing each other in the formed rodlike structure and the repeating length of the monomeric cellobiose unit of molecular chains, respectively. Ratios of the particle length (L) to the radius of gyration (R g) determined by SLS techniques approximately showed the relationship LR g -1 = holding in rigid rods over the entire M w range examined in this study. However, the folding number, defined as the ratio of the average molecular contour length (l) to L, remained at the value of lL -1 ∼ 2, representing an elongated one-folded hairpin structure, until M w ∼ 300 kg mol-1 and increased substantially up to ca 4.9 at the highest M w of 790 kg mol-1. The observed increase in the lL -1 value corresponded well with an increase in the diameter of the formed rod with increasing M w observed in the S-WANS data. The M w dependencies of the translational diffusion coefficient determined via DLS measurements and that of the intrinsic viscosity detected via viscometric techniques also distinctly demonstrated that particles formed by the MC samples dissolved in aqueous solution behave as elongated rigid rods irrespective of M w.
| S-EPMC9404515 | biostudies-literature
Project description:The method of intramolecular coordination number concentration invariance (ICNCI) is used on neutron diffraction with isotopic substitution (NDIS) measurements of aqueous solutions to separate the intra- and intermolecular contributions to the total intensities. Molecular dynamics simulations of corresponding systems are then used to interpret the ICNCI function. It is found that the ICNCI function (characterized by two concentration measurements) is sensitive specifically to intermolecular association and that the molecular dynamics can successfully replicate this function in the cases of the neutral species xylose and pyridine in aqueous solution. ICNCI functions can also be obtained by the addition of a cosolute (such as adding GdmCl or Gdm2SO4 to pyridine solutions). In that case it is found that molecular dynamics can replicate the ICNCI function for the addition of GdmCl to pyridine, but fails to successfully replicate the same function for the addition of Gdm2SO4. This result implies that the interaction of pyridine with guanidinium sulfate is over-estimated in these MD simulations, and is of significant importance to the use of molecular dynamics simulations to elucidate an atomic level understanding of the Hofmeister series.
| S-EPMC3694749 | biostudies-literature
Project description:Classical molecular dynamics simulations and free energy methods have been used to obtain a better understanding of the molecular processes occurring prior to the first nucleation event for calcium phosphate biominerals. The association constants for the formation of negatively charged complexes containing calcium and phosphate ions in aqueous solution have been computed, and these results suggest that the previously proposed calcium phosphate building unit, [Ca(HPO4)3]4-, should only be present in small amounts under normal experimental conditions. However, the presence of an activation barrier for the removal of an HPO4 2- ion from this complex indicates that this species could be kinetically trapped. Aggregation pathways involving CaHPO4, [Ca(HPO4)2]2-, and [Ca(HPO4)3]4- complexes have been explored with the finding that dimerization is favorable up to a Ca/HPO4 ratio of 1:2.
| S-EPMC7011744 | biostudies-literature
Project description:The mercury(II) complexes formed in neutral aqueous solution with glutathione (GSH, here denoted AH(3) in its triprotonated form) were studied using Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) and (199)Hg NMR spectroscopy, complemented with electrospray ionization mass spectrometric (ESI-MS) analyses. The [Hg(AH)(2)](2-) complex, with the Hg-S bond distances at 2.325 ± 0.01 Å in linear S-Hg-S coordination, and the (199)Hg NMR chemical shift at -984 ppm, dominates except at high excess of glutathione. In a series of solutions with C(Hg(II)) ?17 mM and GSH/Hg(II) mole ratios rising from 2.4 to 11.8, the gradually increasing mean Hg-S bond distance corresponds to an increasing amount of the [Hg(AH)(3)](4-) complex. ESI-MS peaks appear at -m/z values of 1208 and 1230 corresponding to the [Na(4)Hg(AH)(2)(A)](-) and [Na(5)Hg(AH)(A)(2)](-) species, respectively. In another series of solutions at pH 7.0 with C(Hg(II)) ?50 mM and GSH/Hg(II) ratios from 2.0 to 10.0, the Hg L(III)-edge EXAFS and (199)Hg NMR spectra show that at high excess of glutathione (?0.35 M) about ?70% of the total mercury(II) concentration is present as the [Hg(AH)(3)](4-) complex, with the average Hg-S bond distance 2.42 ± 0.02 Å in trigonal HgS(3) coordination. The proportions of HgS(n) species, n = 2, 3, and 4, quantified by fitting linear combinations of model EXAFS oscillations to the experimental EXAFS data in our present and previous studies were used to obtain stability constants for the [Hg(AH)(3)](4-) complex and also for the [Hg(A)(4)](10-) complex that is present at high pH. For Hg(II) in low concentration at physiological conditions (pH 7.4, C(GSH) = 2.2 mM), the relative amounts of the HgS(2) species [Hg(AH)(2)](2-), [Hg(AH)(A)](3-), and the HgS(3) complex [Hg(AH)(3)](4-) were calculated to be 95:2:3. Our results are not consistent with the formation of dimeric Hg(II)-GSH complexes proposed in a recent EXAFS study.
| S-EPMC3059209 | biostudies-literature
Project description:Self-assembled structures have attracted much attention for their potential applications in biological and electrochemical studies. Understanding the aggregation mechanism is necessary for utilizing the structures and improving the properties. In this study, the tubular cluster aggregations formed by the 1-dodecyl-3-methylimidazolium salicylate ([C12mim][Sal]) have been studied by molecular dynamics simulations. The rod-like and funnel-shaped structures were observed during the simulations, and finally, the nanotube structure enclosed by a bilayer membrane was formed. For the first time, the point cloud fitting method was used to obtain the axis equation of the tubular cluster. Based on the equation, the structure of tubular clusters was analyzed in detail. The imidazolium ring and anions were distributed at the ionic liquid-water interface, while the dodecyl groups were buried in the nanotube membrane away from the water. Electrostatic interactions between cations and anions played a dominant role in stabilizing the structure of the nanotube. The tubular cluster size, membrane thickness, and permeability of water molecules through the membrane of the cluster were also calculated. Furthermore, the orientation analysis revealed that multitudinous aggregation structures could be formed by the long alkyl chain in aqueous solution, which might be beneficial for the strengthening and separating processes.
| S-EPMC9753178 | biostudies-literature
Project description:The introduction of selective recognition sites toward certain heavy metal ions (HMIs) is a great challenge, which has a major role when the separation of species with similar physicochemical features is considered. In this context, ion-imprinted polymers (IIPs) developed based on the principle of molecular imprinting methodology, have emerged as an innovative solution. Recent advances in IIPs have shown that they exhibit higher selectivity coefficients than non-imprinted ones, which could support a large range of environmental applications starting from extraction and monitoring of HMIs to their detection and quantification. This review will emphasize the application of IIPs for selective removal of transition metal ions (including HMIs, precious metal ions, radionuclides, and rare earth metal ions) from aqueous solution by critically analyzing the most relevant literature studies from the last decade. In the first part of this review, the chemical components of IIPs, the main ion-imprinting technologies as well as the characterization methods used to evaluate the binding properties are briefly presented. In the second part, synthesis parameters, adsorption performance, and a descriptive analysis of solid phase extraction of heavy metal ions by various IIPs are provided.
| S-EPMC10055817 | biostudies-literature