Pál Sipos

The structure of aqueous sodium hydroxide solutions: A combined solution x-ray diffraction and simulation study

To determine the structure of aqueous sodium hydroxide solutions, results obtained from x-ray diffraction and computer simulation (molecular dynamics and Car-Parrinello) have been compared. The capabilities and limitations of the methods in describing the solution structure are discussed. For the solutions studied, diffraction methods were found to perform very well in describing the hydration spheres of the sodium ion and yield structural information on the anions hydration structure. Classical molecular dynamics simulations were not able to correctly describe the bulk structure of these solutions. However, Car-Parrinello simulation proved to be a suitable tool in the detailed interpretation of the hydration sphere of ions and bulk structure of solutions. The results of Car-Parrinello simulations were compared with the findings of diffraction experiments.

Formation of spherical iron(III) oxyhydroxide nanoparticles sterically stabilized by chitosan in aqueous solutions

The interactions between the cationic polymer chitosan (Chit) and iron(III) were investigated. The solution properties were studied by pH-metry, viscometry and dynamic light scattering. Solid state iron(III)-Chit samples were also prepared and characterized by IR spectroscopy and electron microscopy. In aqueous solutions, the precipitation pH of the iron(III) oxyhydroxide (FeOOH) is significantly shifted towards the higher pH values in the presence of Chit indicating that some interaction takes place between the iron(III) and the polymer. However, the additivity of the pH-metric titration curves, the lack of variation both in the viscometric and IR spectra of Chit in the presence and absence of iron(III), indicate the lack of direct complexation between the Chit and ferric ions. Isolated FeOOH nanospheres of 5-10 nm diameter were observed on the transmission electron microscopic pictures of samples obtained from solutions containing iron(III) and Chit, while from DLS measurements hydrodynamic units with a few hundred nm in diameter were identified. Our data support that Chit acts as steric stabilizer and inhibits the macroscopic aggregation of the subcolloidal FeOOH particles. Thus the iron(III)-Chit interactions offer a simple and economic way to fabricate nanometric size FeOOH spheres, morphologically similar to the core of iron(III)-storage protein, ferritin.

Carbonate removal from concentrated hydroxide solutions

Methods for routinely lowering the carbonate content of concentrated aqueous hydroxide solutions [MOH with M+ = Li+, Na+, K+, Cs+ and (CH3)4N+] to analytically negligible levels (⩽ 0.2% of the total alkalinity) are described. No single method was satisfactory for all MOH. Carbonate can be removed from highly concentrated (ca. 50% w/w) NaOH solutions by filtration since Na2CO3 is almost insoluble in this medium. However, for LiOH (ca. 4 M), (CH3)4NOH (ca. 4.5 M) and KOH (ca. 14 M) and less concentrated NaOH (<10 M), treatment with excess solid CaO followed by filtration gave the best results. For CsOH, which may be seriously contaminated with carbonate, the only satisfactory procedure was treatment of very concentrated solutions with excess solid Ba(OH)2. Residual calcium and barium concentrations in the decarbonated solutions were at trace levels.

Quantification of punctate iron sources using magnetic resonance phase

Iron‐mediated tissue damage is present in cerebrovascular and neurodegenerative diseases and neurotrauma. Brain microbleeds are often present in these maladies and are assuming increasing clinical importance. Because brain microbleeds present a source of pathologic iron to the brain, the noninvasive quantification of this iron pool is potentially valuable. Past efforts to quantify brain iron have focused on content estimation within distributed brain regions. In addition, conventional approaches using “magnitude” images have met significant limitations. In this study, a technique is presented to quantify the iron content of punctate samples using phase images. Samples are modeled as magnetic dipoles and phase shifts due to local dipole field perturbations are mathematically related to sample iron content and radius using easily recognized geometric features in phase images. Phantoms containing samples of a chitosan‐ferric oxyhydroxide composite (which serves as a mimic for hemosiderin) were scanned with a susceptibility‐weighted imaging sequence at 11.7 T. Plots relating sample iron content and radius to phase image features were compared to theoretical predictions. The primary result is the validation of the technique by the excellent agreement between theory and the iron content plot. This research is a potential first step toward quantification of punctate brain iron sources such as brain microbleeds. Magn Reson Med, 2010.

Rod-like iron(III) oxyhydroxide particles in iron(III)-polysaccharide solutions☆

The interaction of iron(III) with different anionic polyssacharides has been studied by pH-metric, UV-vis, Fourier transform infrared, viscometric, and conductometric methods. The formation of water-soluble compounds containing surprisingly high numbers of iron(III) ions even at physiological pH has been observed. The complex formation involves carboxylate, sulfonate, and probably alcoholic hydroxylate moieties. The metal binding starts in the acidic pH r region with the complex precipitating at 3.5 ≤ pH ≤ 6. The precipitate dissolves at pH > 6. The compositions of the complexes formed at pH 7 were found to be L[Fe(OH)3]n, where L is the repeating unit of the polymer. The maximum value of n proved to be dependent not only on the coordination ability, but also on the major mass of the ligands. Viscometric and conductometric data suggest that the structure-determining element of these complexes is the polyssacharide rather than an iron oxyhydroxide cluster. Their solution structure can be described as independent rod-like particles comprising an unfolded polysaccharide backbone and polymerized iron(III)-oxyhydroxide particles.

Mechanochemically assisted synthesis of pristine Ca(II)Sn(IV)-layered double hydroxides and their amino acid intercalated nanocomposites

Syntheses of Ca(II)Sn(IV)-layered double hydroxides (LDHs) are attempted by the traditional co-precipitation as well as mechanochemical methods. Both the co-precipitation method and the one-step milling operation proved to be unsuccessful; these methods only produced physical mixtures of hydroxides and carbonates of the two metal ions. However, a two-step milling operation (dry milling followed by milling in the presence of minute amount of water) led to successful synthesis, verified by a range of characterisation methods. Surprisingly, it was found that ball-milling was not even necessary; the reaction proceeded on manual grinding of the components in an agate mortar with a pestle. The preparation of nanocomposites through intercalation of the anions of cystine or valine into Ca(II)Sn(IV)-LDH could also be achieved by the two-step milling method verified again by a range of instrumental methods.

Multinuclear NMR and molecular modelling investigations on the structure and equilibria of complexes that form in aqueous solutions of Ca2+ and gluconate

Complexation of d-gluconate (Gluc(-)) with Ca(2+) has been investigated via (1)H, (13)C and (43)Ca NMR spectroscopy in aqueous solutions in the presence of high concentration background electrolytes (1MI4M (NaCl) ionic strength). From the ionic strength dependence of its formation constant, the stability constant at 6pH11 and at I-->0M has been derived (logK(1,1)(0)=1.8+/-0.1). The protonation constant of Gluc(-) at I=1M (NaCl) ionic strength was also determined and was found to be logK(a)=3.24+/-0.01 ((13)C NMR) and logK(a)=3.23+/-0.01 ((1)H NMR). It was found that (1)H and (13)C NMR chemical shifts upon complexation (both with H(+) and with Ca(2+)) do not vary in an unchanging way with the distance from the Ca(2+)/H(+) binding site. From 2D (1)H-(43)Ca NMR spectra, simultaneous binding of Ca(2+) to the alcoholic OH on C2 and C3 was deduced. Molecular modelling results modulated this picture by revealing structures in which the Gluc(-) behaves as a multidentate ligand. The five-membered chelated initial structure was found to be thermodynamically more stable than that derived from a six-membered chelated initial structure.

Ultrasonically-enhanced mechanochemical synthesis of CaAl-layered double hydroxides intercalated by a variety of inorganic anions

CaAl-layered double hydroxides (CaAl-LDHs) were synthesised with various interlayer anions (CO3(2-), F(-), Cl(-), Br(-) and I(-)) by mechanochemical pre-treatment followed by ultrasonic irradiation in aqueous media. The parameters of the syntheses (duration of pre-milling and sonication, quality of the aqueous media, temperature) were altered in order to optimise the procedure and to understand the formation of LDH and other secondary products. The products were characterised by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The optimisation resulted in close-to-phase-pure CaAl-LDHs, not only with carbonate and chloride interlayer anions, but the hard-to-intercalate bromide and iodide as well.

Raman, IR, and 27Al-MAS-NMR Spectroscopic Studies of Sodium (Hydroxy)Aluminates

A series of solid sodium (hydroxy)aluminates has been prepared from highly caustic aqueous sodium aluminate solutions. The coordination geometry of the aluminum in these compounds was established by 27Al magic angle spinning nuclear magnetic resonance (27Al-MAS-NMR) spectroscopy and was used to identify the Raman and IR vibration frequencies characteristic of tetrahedral (Raman: 440 cm−1; IR: 823 cm−1 and 540 cm−1) and octahedral (Raman: 490–500 cm−1; IR: 728 cm−1) aluminum sites. The vibrational spectra of these solids differ markedly from those observed for concentrated aqueous solutions, and it appears that solid-state vibrational spectra cannot be used to predict the structure of aluminate species existing in solutions.

205TL-NMR and UV-Visible spectroscopic determination of the formation constants of aqueous thallium(I) hydroxo-complexes

The hydrolysis of T1(I) has been studied at 25°C using205T1-NMR spectroscopy and UV-Vis spectrophotometry in aqueous solutions with ionic strengths maintained by NaC104 at 2, 4, 6, and 8M. The formation constant and the spectral characteristics for the hydroxo complex, T10Hℴ have been determined. At high hydroxide ion concentrations there is clear evidence from the UV-Vis data for the formation of a T1(OH)2-species. The spectrum and an estimated formation constant for this second hydroxo complex are also reported.