An Investigation of the Digitized Raman Band Profiles of Aqueous Mg(ClO4)2 - NaSCN Solutions

Abstract

Raman spectra, together with factor analysis and band deconvolution procedure, have been used to study formation of magnesium thiocyanate complexes in aqueous solutions at ambient and elevated temperatures. The total salt concentration in solutions, containing different mole ratio of Mg²⁺ to SCN, varied between 3.4 and 7.5 mol dm^?3. Factor analyses indicated that two linearly independent scattering components in the band envelopes, recorded in the V₁ and v₃ stretching regions of SCN, for all solutions with total salt concentration of 3.4 mol dm^?3. The appearance of a pseudo-isosbestic point in the area normalized spectra supported this result, as well as the baud resolution procedure. The latter revealed the third scattering component in the spectra of solutions with total salt concentration above 3.5 mol dm^?3 Resolved components have been assigned to the free thiocyanate, the 1:1 and 1:2 magnesium thiocyanate complexes. The equilibrium constant K_c of the 1:1 complex is of an order of 10^?1 mol dm^?3.     

Alkane oxidation by the system ‘tert‐butyl hydroperoxide–[Mn2L2O3][PF6]2 (L = 1,4,7‐trimethyl‐1,4,7‐triazacyclononane)–carboxylic acid’

The kinetics of cyclohexane (CyH) oxygenation with tert‐butyl hydroperoxide (TBHP) in acetonitrile at 50 °C catalysed by a dinuclear manganese(IV) complex 1 containing 1,4,7‐trimethyl‐1,4,7‐triazacyclononane and co‐catalysed by oxalic acid have been studied. It has been shown that an active form of the catalyst (mixed‐valent dimeric species ‘Mn^IIIMn^IV’) is generated only in the interaction between complex 1 and TBHP and oxalic acid in the presence of water. The formation of this active form is assumed to be due to the hydrolysis of the Mn? O? Mn bonds in starting compound 1 and reduction of one Mn^IV to Mn^III. A species which induces the CyH oxidation is radical tert‐BuO ^. generated by the decomposition of a monoperoxo derivative of the active form. The constants of the equilibrium formation and the decomposition of the intermediate adduct between TBHP and 1 have been measured: K = 7.4 mol^?1 dm³ and k = 8.4 × 10^?2 s^?1, respectively, at [H₂O] = 1.5 mol dm^?3 and [oxalic acid] = 10^?2 mol dm^?3. The constant ratio for reactions of the monomolecular decomposition of tert‐butoxy radical (tert‐BuO ^. → CH₃COCH₃ + CH) and its interaction with the CyH (tert‐BuO ^. + CyH → tert‐BuOH + Cy ^. ) was calculated: 0.26 mol dm^?3. One of the reasons why oxalic acid accelerates the oxidation is due to the formation of an adduct between oxalic acid and 1 (K ≈ 10³ mol^?1 dm³). Copyright © 2007 John Wiley & Sons, Ltd.     

Calorimetric study of proton ordering in hexagonal ice catalyzed by hydrogen fluoride

Heat capacities of hexagonal ices doped with 2.6, 26 and 260 m mol dm^?3 HF were measured with an adiabatic calorimeter. The HF doping accelerated proton ordering which has been known to take place sluggishly around 100 K. The ice containing 26 m mol dm^?3 HF showed the largest excess entropy ((0.102±0.01) J K^?1 mol^?1) and the shortest relaxation time. The relaxation time at 90 K was about $\text{1}\text{30}$ of that of the pure ice I_h at the same temperature. The activation enthalpies obtained were the same for all of the doped ices, (23.5±2.0) J mol^?1, which is approximately equal to the activation energy of the mobility of the Bjerrum L-defect.     

蓝宝石(α-Al_2O_3:Fe~(3+))体系基态分裂与局域晶格畸变的研究

2002年Scholz和Buzaré对蓝宝石晶体中Fe3+离子的基态分裂重新进行了EPR实验测量和研究,他们的初步分析表明在蓝宝石晶体中Fe3+离子的6A1基态分裂有可能同时与两个方向的畸变角(θ和φ)有关.本文采用对角化d5组态在C3点群对称下的252×252完全能量矩阵的方法,对蓝宝石晶体中Fe3+离子的光谱和EPR谱进行了系统的研究.计算结果表明蓝宝石体系中Fe3+离子的6A1基态分裂确实将明显依赖于两个方向的畸变角θ和φ,这一理论结果与Scholz和Buzaré等的实验相符合.同时,通过拟合Fe3+离子在蓝宝石体系中的实验光谱和EPR参量,确定了蓝宝石晶体中(FeO6)9团簇局域晶格畸变角θi的范围.     

Effect of Solvent Polarity on Fluorescence Quenching of New Indole Derivatives by CCl4

ABSTRACT

The fluorescence quenching of solutes 3-[5′-methyl-3′-phenylindol-2′-yl]-s-triazolo [3,4-b] [1,3,4] thiadiazol-6(5H)-thione (MPITTT) and 3-phenyl-2,5-bis-[thiosemicarbazido] indole (PbisTI) by carbon tetrachloride (CCl₄) in dioxane and acetonitrile mixtures has been studied at room temperature by steady-state fluorescence measurements. The positive deviation from linearity has been observed in the Stern–Volmer (S-V) plots for both fluorophores in different composition of mixed solvents even at moderate CCl₄ concentration (0.10 mol dm^?3). Various quenching parameters of the quenching processes have been determined using the extended S-V equation and have been found to be dependent on the solvent polarity. Further, with the use of the finite sink approximation model, it is concluded that the bimolecular quenching reactions are diffusion limited, and the distance parameter R′ and mutual diffusion coefficient D are estimated independently.     

Effect of Lumophore and Plasticiser Concentration on The Heterogeneity of Oxygen Quenching in Thin Film Oxygen Sensors

Kinetic heterogeneity of the luminescence decay and oxygen quenching of Pt and Pd octaethylporphyrin/ethyl cellulose (OEP/EC) thin film oxygen sensors has been investigated with respect to (a) concentration of lumophore and (b) addition of plasticiser. The source of kinetic heterogeneity shown by PtOEP films under N₂ is a monomer–dimer equilibrium in which the dimer luminescence decays with k = 0.0527×10⁶ s⁻¹ and the monomer luminescence with k = 0.0101×10⁶ s⁻¹ and K _D = 790 (±20) mol dm⁻³. For PdOEP/EC films there is no detectable aggregation and luminescence decays under N₂ show good fits to single exponential curve fits at all concentrations studied. The addition of either tripbutyl phosphate or dimethylphthalate as plasticiser does not decrease kinetic heterogeneity for oxygen quenching of luminescence in the films.     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.     

Nature of the transient species formed in the pulse radiolysis of 4‐hydroxybenzyl alcohol in aqueous solutions: observation of equilibrium in the reaction of OH‐adducts with HPO ions

Reactions of ^. OH/O ^.? radicals, H‐atoms as well as specific oxidants such as N and Cl radicals with 4‐hydroxybenzyl alcohol (4‐HBA) in aqueous solutions have been investigated at various pH values using the pulse radiolysis technique. At pH 6.8, ^. OH radicals were found to react with 4‐HBA (k = 6 × 10⁹ dm³ mol^?1 s^?1) mainly by contributing to the phenyl moiety and to a minor extent by H‐abstraction from the ? CH₂OH group. ^. OH radical adduct species of 4‐HBA, i.e., ^. OH‐(4‐HBA) formed in the addition reaction were found to undergo dehydration to give phenoxyl radicals of 4‐HBA. Decay rate of the adduct species was found to vary with pH. At pH 6.8, decay was very much dependent on phosphate buffer ion concentrations. Formation rate of phenoxyl radicals was found to increase with phosphate buffer ion concentration and reached a plateau value of 1.6 × 10⁵ s^?1 at a concentration of 0.04 mol dm^?3 of each buffering ion. It was also seen that ^. OH‐(4‐HBA) adduct species react with HPO ions with a rate constant of 3.7 × 10⁷ dm³ mol^?1 s^?1 and there was no such reaction with H₂PO ions. However, the rate of reaction of ^. OH‐(4‐HBA) adduct species with HPO ions decreased on adding KH₂PO₄ to the solution containing a fixed concentration of Na₂HPO₄ which indicated an equilibrium in the H⁺ removal from ^. OH‐(4‐HBA) adduct species in the presence of phosphate ions. In the acidic region, the ^. OH‐(4‐HBA) adduct species were found to react with H⁺ ions with a rate constant of 2.5 × 10⁷ dm³ mol^?1 s^?1. At pH 1, in the reaction of ^. OH radicals with 4‐HBA (k = 8.8 × 10⁹ dm³ mol^?1 s^?1), the spectrum of the transient species formed was similar to that of phenoxyl radicals formed in the reaction of Cl radicals with 4‐HBA at pH 1 (k = 2.3 × 10⁸ dm³ mol^?1 s^?1) showing that ^. OH radicals quantitatively bring about one electron oxidation of 4‐HBA. Reaction of ^. OH/O ^.? radicals with 4‐HBA by H‐abstraction mechanism at neutral and alkaline pH values gave reducing radicals and the proportion of the same was determined by following the extent of electron transfer to methyl viologen. H‐atom abstraction is the major pathway in the reaction of O ^.? radicals with 4‐HBA compared to the reaction of ^. OH radicals with 4‐HBA. At pH 1, transient species formed in the reactions of H‐atoms with 4‐HBA (k = 2.1 × 10⁹ dm³ mol^?1 s^?1) were found to transfer electrons to methyl viologen quantitatively. Copyright © 2009 John Wiley & Sons, Ltd.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Self‐association,tautomerism and E–Z isomerization of isatin–phenylsemicarbazones – spectral study and theoretical calculations

The self‐association and tautomerism of (E)‐isatin‐3‐4‐phenyl(semicarbazone) Ia and (E)‐N‐methylisatin‐3‐4‐phenyl(semicarbazone) IIa were investigated in solvents of various polarity. In weakly interacting non‐polar solvents, such as CHCl₃ and benzene, phenylsemicarbazone concentrations above 1×10^?5 mol dm^?3 result in the formation of dimers or higher aggregates of E‐isomers Ia and IIa . This aggregate formation prevents room temperature E–Z isomerization of Ia and IIa to more stable Z‐isomers. In contrast to the situation in non‐polar solvents, E–Z isomerization from the monomeric form of phenylsemicarbazone Ia and IIa E‐isomers occurs in highly interactive polar solvents including MeOH and DMF only at temperatures above 70 °C. Moreover, decrease in phenylsemicarbazone concentration below 1×10^?4 mol dm^?3 in these highly solute–solvent interacting systems leads to aggregate dissociation, and a new hydrazonol tautomeric form with a high degree of conjugation predominates in these solutions. Theoretical calculations confirm obtained experimental results. Copyright © 2013 John Wiley & Sons, Ltd.     

One-step microfabrication of fused silica by laser ablation of an organic solution

2 and an acetone solution containing pyrene at a concentration of 0.4 mol/dm³. The threshold fluence was 240 mJ/cm², which is about one-fortieth lower than that obtained with conventional KrF laser ablation. Received: 7 September 1998/Accepted: 9 September 1998     

Effect of Hydrolysis Conditions on the Direct Formation of Nanoparticles of Ceria–Zirconia Solid Solutions from Acidic Aqueous Solutions

The effect of the cation concentration, hydrolysis temperature, and composition in the CeO₂–ZrO₂ system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO₂ were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm³ by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm³ at the starting composition of 50 mol% ZrO₂ under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH₄)₂Ce(NO₃)₆. Ceria–zirconia solid solutions containing large amount of ZrO₂ maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h.     

Nitrosation of dialkylhydroxylamines,and computational and NMR investigations of the interconversion of conformational isomers of N‐nitroso‐dimethylhydroxylamine

The effect of acidity upon the rate of nitrosation of N‐benzyl,O‐methylhydroxylamine ( 3 ) in 1:1 (v/v) H₂O/MeOH at 25 °C has been investigated. The pseudo‐first‐order rate constant (k_obs) for loss of HNO₂ as the limiting reagent decreases as [H₃O⁺] increases. This is compatible with two parallel reaction channels (Scheme 2 ). One involves the direct reaction of the free hydroxylamine with HNO₂ (k₁ = 1.4 × 10² dm³ mol^?1 s^?1, 25 °C) and the other involves the reaction of the free hydroxylamine with NO⁺ (k₂ = 5.9 × 10⁹ dm³ mol^?1 s^?1). In contrast, there is only a very slight increase in k_obs with increasing [H₃O⁺] for nitrosation of N,O‐dimethylhydroxylamine ( 4 ) in dilute aqueous solution at 25 °C to give N‐nitroso‐dimethylhydroxylamine, 5 . This also fits a two‐channel mechanism (Scheme 3 ). Again, one involves the nitrosation of the free base by NO⁺ (k₂ = 8 × 10⁹ dm³ mol^?1 s^?1, 25 °C) but the other channel now involves catalysis by chloride (k₃ = 1.3 × 10⁸ dm³ mol^?1 s^?1). Arising from these results, we propose an estimate of pK_a ～ ?5 for protonated nitrous acid, (O = N? OH), which is appreciably different from the literature value of +1.7. The interconversion of cis and trans conformational isomers of 5 has been investigated by temperature‐dependent NMR spectroscopy in CDCl₃, methanol‐d₄, toluene‐d₈ and dimethyl sulfoxide‐d₆. Enthalpies and entropies of reaction and of activation have been determined and compared with computational values obtained at the B3LYP/6‐31G* level of theory. The cis form is slightly more stable at normal temperatures and no solvent effects upon the thermodynamics or kinetics of the conformational equilibrium were predicted computationally or detected experimentally. In addition, key geometric parameters and dipole moments have been calculated for the cis and trans forms, and for the lowest energy transition structure for their interconversion, in the gas phase and in chloroform. These results indicate electronic delocalisation in the ground states of 5 which is lost in the transition structure for their interconversion. Copyright © 2010 John Wiley & Sons, Ltd.     

Phase-matched third-harmonic generation of Nd: Glass-laser picosecond pulses in a new cyanine-dye solution

The phase-matched direct tripling of picosecond light pulses of a mode-locked Nd: glass laser in a new cyanine dye PMC is studied. The solvents trifluoroethanol (TFE) and hexafluoroisopropanol (HFIP) are applied. The S ₀–S ₁ absorption peak of the dye is around =480 nm and the absorption cross section at the third-harmonic wavelength of ₃=351.3 nm is only ₃1×10^–19 cm². Phase-matching occurred at concentrations of C_PM=0.0874 mol/dm³ in HFIP and 0.1088 mol/dm³ in TFE. A third-harmonic energy conversion efficiency of _E0.01 was achieved at a pump-laser peak intensity of I _0L2.5×10¹¹ W/cm² in a 5 mm long sample of PMC in TFE. The conversion efficiency is limited by destruction of phase-matching due to the intensity-dependent nonlinear refractive index of the dye solutions.     

Effect of sodium salt addition upon electrochemical behavior of natural graphite

Despite the reported enhanced electrochemical behavior of graphite anodes due to the addition of NaClO₄ salts in to the electrolytes used in lithium battery applications, a detailed investigation upon the effect of addition of NaPF₆ salt in an electrolyte containing 1 M LiPF₆ in 1:1 V/V EC:DEC has resulted in inferior electrochemical behavior of graphite, i.e., quite contrast to the reported behavior of improved effects of addition of NaClO₄ into 1 M LiClO₄ solution, the addition of 0.22 mol dm⁻³ NaPF₆ salt has been found to reduce the capacities of lithium-ion cells containing 1 M LiPF₆ in 1:1 V/V EC:DEC. Towards this study, cells fabricated with and without the addition of 0.22 mol dm⁻³ NaPF₆ in 1 M LiPF₆ (1:1 V/V EC:DEC) were subjected to a systematic charging at a constant C/10 rate and discharging of cells at four different rates, viz., C/5, C/2 and C rates at the end of every 5 cycles. The observed results of the charge-discharge studies up to 15 cycles are discussed in this preliminary communication.     

Features of Propene Oxidation in Argon,Carbon Dioxide and Water Vapor Media at a High Density of Reagents

The features of propene oxidation in high-density mixtures of C₃H₆/O₂ ([C₃H₆]₀ = 0.23–0.25 mol/dm³, [O₂]₀ = 0.76–0.82 mol/dm³), diluted with argon, carbon dioxide and water vapor at uniform heating (1 K/min) to T ≤ 620 K are investigated for the first time. From the time dependences of reaction mixtures temperature it is found that propene self-ignition occurs at 465 K and does not depend on the nature of the diluent. Using mass spectrometry analysis it is demonstrated that in the composition of the products of propene oxidation in the Ar and CO₂ medium predominate methanol, acetaldehyde, acetone, acetic acid and formaldehyde; in the oxidation in the H₂O medium, only small amof O₂ in the oxidation of propene increases in ounts of these substances were registered. Degree of consumption the following order: CO₂ ? Ar < H₂O, which is a consequence of the involvement of CO₂ and H₂O molecules in chemical transformations. Mechanisms of the observed processes are discussed.     

Adsorption of mercaptopurine drug on the BN nanotube,nanosheet and nanocluster: a density functional theory study

ABSTRACT

We have investigated the interaction of mercaptopurine (MP) drug with BN nanotube, nanosheet and nanocluster using density functional theory calculations in the gas phase, and aqueous solution. We predicted that the MP drug tends to be physically adsorbed on the surface of BN nanosheet with an adsorption energy (E_ad) about ?3.2?kcal/mol. The electronic properties of BN nanosheet are not affected by the MP drug, and this sheet is not a sensor. But the electronic properties of BN nanotube and nanocluster are significantly sensitive to this drug in both gas phase, and aqueous solution. The BN nanocluster suffers from a long recovery time (8.8?×?10⁸?s) because of a strong interaction (E_ad?=??28.6?kcal/mol), and this cluster is not a proper sensor for MP detection. But the BN nanotube benefits from a short recovery time about 49.5?s at room temperature, and may be a promising candidate for application in the MP sensors. The water solvent decreases the strength of interaction between the BN nanotube, and MP drug, but it does not affect the electronic sensitivity of the nanotube sensibly.     

Microwave spectra of phosphoryl trifluoride in vibrationally excited states

The ground-state rotational spectra of ¹⁶OPF₃ and ¹⁸OPF₃ have been recorded and analysed to yield a structure and accurate centrifugal distortion constants.

The pure rotational spectrum of ¹⁶OPF₃ has been recorded and analysed for five of the molecule's vibrationally excited states. The analysis of the ν₅ = 1 and ν₆ = 1 states is discussed in detail and values of ζ₅₅ ^z and ζ₆₆ ^z have been obtained. In addition, information is obtained about the elusive A rotational constant for ν₆ = 1 due to an accidental near degeneracy which yields the value A _ν=4797·86 MHz.

Some of the information obtained is used to derive the harmonic force field for the OPF₃ molecule. The use of ground-state distortion constants instead of their equilibrium values is discussed.     

Synthesis of novel amorphous calcium carbonate by sono atomization for reactive mixing

Droplets of several micrometers in size can be formed in aqueous solution by atomization under ultrasonic irradiation at 2 MHz. This phenomenon, known as atomization, is capable of forming fine droplets for use as a reaction field. This synthetic method is called SARM (sono atomization for reactive mixing). This paper reports on the synthesis of a novel amorphous calcium carbonate formed by SARM. The amorphous calcium carbonate, obtained at a solution concentration of 0.8 mol/dm³, had a specific surface area of 65 m²/g and a composition of CaCO₃•0.5H₂O as determined using thermogravimetric/differential thermal analysis (TG-DTA). Because the ACC had a lower hydrate composition than conventional amorphous calcium carbonate (ACC), the ACC synthesized in this paper was very stable at room temperature.     

Spectrophotometric and 27‐Al NMR Characterization of Aluminum(III) Complexes with l‐Histidine

Abstract

The complex formation between l‐histidine (HHis) and aluminum(III) ion in water solutions was studied by UV spectrophotometric and 27‐Al NMR measurements at 298 K. UV spectra were measured on solutions in which the total concentration of histidine was from 15.0 to 50.0 mmol/dm³ and the concentration ratio of histidine to aluminum was varied from 3∶1 to 10∶1 in the pH range between 4.2 and 6.0. The spectra were taken in the wavelength interval 240–340 nm. Nonlinear least‐squares treatment of the spectrophotometric data indicates the formation of the complexes Al(HHis)³⁺, Al(His)²⁺, Al(HHis)His²⁺, and Al₂(OH)His⁴⁺ with the overall formation constants β_p,q,r: log β_1,1,1=11.90±0.04, log β_1,1,0=7.25±0.08, log β_1,2,1=20.1±0.1, and log β_2,1,1=5.92±0.12 (p, q, r are stoichiometric indices for metal, ligand, and proton, respectively). ²⁷Al‐NMR spectra were taken on solutions with the concentration of aluminum 50 mmol/dm³ and that of histidine 250 mmol/dm³. In the pH interval 5.0–6.1, two resonances at 9.5 ppm and 12.0 ppm were assigned to Al(HHis)²⁺ and Al(HHis)(His)²⁺ (or Al(OH)(HHis)₂ ²⁺), respectively.