Solid–liquid phase equilibria in the systems K2SO4–MSO4–H2O (M = Co,Ni, Cu) from ambient to enhanced temperatures

Reviewing the literature solubility isotherms in the ternary systems K₂SO₄–MSO₄–H₂O (M = Co, Ni, Cu, Zn) revealed a lack at ambient temperatures. The solid–liquid phase equilibria have been determined in the systems K₂SO₄–MSO₄–H₂O (M = Co, Ni, Cu) at T = 313 K. With increasing bivalent metal sulfate concentration, the solubility of potassium sulfate rises until the two-salt point is reached. Reciprocally, the solubility of the bivalent metal sulfate hydrates (CoSO₄·7H₂O, α-NiSO₄·6H₂O, CuSO₄·5H₂O) increases with rising potassium sulfate concentration. In all three systems the double salts of Tutton's type K₂SO₄·MSO₄·6H₂O (M = Co, Ni, Cu) are formed.     

Stimulated Raman scattering measurements of H2 vibration–vibration transfer

We present a new set of V–V rate coefficients for vibrational levels 0–5 in H₂ at 300 K, measured using a stimulated Raman–spontaneous Raman pump/probe apparatus. The measured rate of the non-resonant process, H₂(v = 1) + H₂(v = 1) → H₂(v = 0) + H₂(v = 2), is consistent with the previously reported experimental value of Kreutz et al. However, semi-classical predictions of such non-resonant processes, using the identical inter-molecular potential and methodology to that given by Cacciatore and Billing, results in rates which are too slow, by a factor of approximately 3. For the “resonant” V–V process, H₂(v = 1) + H₂(v = 0) → H₂(v = 0) + H₂(v = 1), the semi-classical rate is found to be too slow by an even larger factor, of approximately 30, compared to the experimental rate, but consistent with the previously reported experimental result of Farrow and Chandler. Further, unlike the semi-classical model prediction in which the (1, 1 → 2, 0) process rate is predicted to exceed that of the (1, 0 → 0, 1) process, the experimental data shows it to be a factor of approximately 2.5 less, suggesting that semi-classical methods that treat the rotational motion classically are unsuitable for the highly anharmonic H₂ molecule. The ratio of pure rotation and rotation–vibration Raman cross sections for scattering from levels 0 and 1 is also determined, with results which agree with calculations of Schwartz and LeRoy, but are somewhat larger than previous experimental results of Cureton.     

Rapid access to homoallylic alcohols via Pd(OAc)2 catalyzed Barbier type allylation in presence of DMAP

DMAP was found to accelerate significantly the rate of Pd(OAc)₂ catalyzed Barbier type allylation of carbonyl compounds by allylbromide using SnCl₂·2H₂O as reducing agent. Both aldehyde as well as ketones produced excellent yields within a short reaction time in the presence of 3 mol % of Pd(OAc)₂ and 12 mol % of DMAP at room temperature. Aldehydes could be allylated within 5–10 min whereas, in case of ketones, the reaction completes in 45–120 min.     

Determination of mercury species by the diffusive gradient in thin film technique and liquid chromatography – atomic fluorescence spectrometry after microwave extraction

A diffusive gradient in thin films technique (DGT) was combined with liquid chromatography (LC) and cold vapor atomic fluorescence spectrometry (CV-AFS) for the simultaneous quantification of four mercury species (Hg²⁺, CH₃Hg⁺, C₂H₅Hg⁺, and C₆H₅Hg⁺). After diffusion through an agarose diffusive layer, the mercury species were accumulated in resin gels containing thiol-functionalized ion-exchange resins (Duolite GT73, and Ambersep GT74). A microwave-assisted extraction (MAE) in the presence of 6 M HCl and 5 M HCl (55 °C, 15 min) was used for isolation of mercury species from Ambersep and Duolite resin gels, respectively. The extraction efficiency was higher than 95.0% (RSD 3.5%). The mercury species were separated with a mobile phase containing 6.2% methanol + 0.05% 2-mercaptoethanol + 0.02 M ammonium acetate with a stepwise increase of methanol content up to 80% in the 16th min on a Zorbax C18 reverse phase column. The LODs of DGT–MAE–LC–CV-AFS method were 38 ng L⁻¹ for CH₃Hg⁺, 13 ng L⁻¹ for Hg²⁺, 34 ng L⁻¹ for C₂H₅Hg⁺ and 30 ng L⁻¹ for C₆H₅Hg⁺ for 24 h DGT accumulation at 25 °C.     

Hydrogen permeability of 2.5 μm palladium–silver membranes deposited on ceramic supports

The permeability of hydrogen selective Pd-based membranes was tested in different experimental conditions. The membranes were obtained by depositing palladium–silver films onto ceramic porous supports, with film composition of about 20 wt% of silver and thicknesses of about 2.5 μm. Their permeance was measured at 400 °C at total trans-membrane pressures between 0.2 and 6 bar, using pure feeds of H₂ and N₂, as well as H₂/N₂ and H₂/CO mixtures; the temperature dependence of permeability was investigated using pure H₂ feeds at 300, 400 and 500 °C. The membranes exhibit a very attractive behavior, maintaining a virtually infinite selectivity throughout the testing, with permeance values among the highest values reported in literature for similar membranes. Permeation of pure hydrogen accurately follows Sieverts’ law and confirms the presence of a chemisorption–dissociation–diffusion mechanism, characterised by the transport of atomic hydrogen through the Pd–Ag layer as the limiting step. In the case of H₂/N₂ mixtures, the high membrane permeance originates also significant concentration polarization phenomena resulting in apparent deviations from Sieverts’ behavior; the presence of CO in the feed may reduce hydrogen permeability even by 75%, although this effect is shown to be fully reversible after a subsequent air treatment at 400 °C. The temperature dependence of the membrane permeability is of Arrhenius type, with an activation energy of about 17 kJ/mol, that is, close to what is reported for Pd–Ag membranes following Sieverts’ behavior.     

Revision of iron(III)–citrate speciation in aqueous solution. Voltammetric and spectrophotometric studies

A detailed study of iron (III)–citrate speciation in aqueous solution (θ = 25 °C, I_c = 0.7 mol L⁻¹) was carried out by voltammetric and UV–vis spectrophotometric measurements and the obtained data were used for reconciled characterization of iron (III)–citrate complexes. Four different redox processes were registered in the voltammograms: at 0.1 V (pH = 5.5) which corresponded to the reduction of iron(III)–monocitrate species (Fe:cit = 1:1), at about −0.1 V (pH = 5.5) that was related to the reduction of FeL₂⁵⁻, FeL₂H⁴⁻ and FeL₂H₂³⁻ complexes, at −0.28 V (pH = 5.5) which corresponded to the reduction of polynuclear iron(III)–citrate complex(es), and at −0.4 V (pH = 7.5) which was probably a consequence of Fe(cit)₂(OH)_x species reduction. Reversible redox process at −0.1 V allowed for the determination of iron(III)–citrate species and their stability constants by analyzing E_p vs. pH and E_p vs. [L⁴⁻] dependence. The UV–vis spectra recorded at varied pH revealed four different spectrally active species: FeLH (log β = 25.69), FeL₂H₂³⁻ (log β = 48.06), FeL₂H⁴⁻ (log β = 44.60), and FeL₂⁵⁻ (log β = 38.85). The stability constants obtained by spectrophotometry were in agreement with those determined electrochemically. The UV–vis spectra recorded at various citrate concentrations (pH = 2.0) supported the results of spectrophotometric–potentiometric titration.     

Triazole-bridged magnetic M(II) assemblies (M = Co,Ni) capped with the end-on terephthalate dianion involving multi-intermolecular contacts

Two dimeric complexes [M₂(atrz)₃(H₂O)₄(tp)₂] · 11H₂O [M = Co(1 · 11H₂O), Ni(2 · 11H₂O); tp = terephthalate, atrz = 4-aminotriazole] were constructed from triply-bridged triazole ligands and terminal tp groups. Interestingly tp behaves as a capping group in an end-on fashion, which is a rare example for tp-related systems. Among the dinuclear assemblies, three types of intermolecular interactions (hydrogen bond, face-to-face π–π and edge-to-face CH–π contacts) as well as intramolecular hydrogen bonding are observed, eventually leading to the formation of a 3D network. Magnetic data show that moderate antiferromagnetic interactions between the two metal centers communicate through triazole groups, and non-negligible interdimer antiferromagnetic couplings are also involved in this system.     

Synthesis,structure and properties of a series of scorpionate oxovanadium(IV)–carboxylate complexes

A series of oxovanadium(IV) complexes: TpVO(pzH)(2,4-Cl–C₆H₃–OCH₂COO) (1), TpVO(pzH)(C₆H₅–OCH₂COO) (2), TpVO(pzH)(p-Cl–C₆H₄–COO) (3), TpVO(pzH)(3,5-NO₂–C₆H₃–COO) (4), Tp∗VO(pzH∗)(p-Cl–C₆H₄–COO) (5) and Tp∗VO(pzH∗)(p-Cl–C₆H₄–COO) · CH₃OH (6) (Tp = hydrotris(pyrazolyl)borate, pzH = pyrazole, Tp∗ = hydrotris(3,5-dimethylpyrazolyl)borate, pzH∗ = 3,5-dimethylpyrazole) were synthesized and their crystal structures were determined by X-ray diffraction. In all the complexes, the vanadium ions are in a distorted-octahedral environment with a N₄O₂ donor set. Hydrogen bonding interaction exists in each complex. Complexes 1 and 2 are hydrogen-bonded dimers. Dimeric units of 2 are connected to one another via weak inter-molecular C–H···O interactions to form a 2D network on the bc-face. In 3–6 there exist intramolecular N–H···O hydrogen bonds between the neutral pyrazole/3,5-dimethylpyrazole and the uncoordinated carboxyl oxygen atom. In addition, the catalytic activity of complex 2 in a bromination reaction in phosphate buffer with phenol red as a trap was evaluated by UV–Vis spectroscopy. Furthermore, the elemental analyses, IR spectra and thermal stabilities were recorded.     

Organogold(III) complexes containing chelating bis(amidate) ligands: Synthesis,characterisation and biological activity

Reactions of cycloaurated gold(III) dichloride complexes, with 1,2-C₆H₄(NHCOMe)₂ and silver(I) oxide, or with C₂H₄(NHSO₂Tol)₂ (Tol = p-tolyl) or 1,2-C₆H₄(NHSO₂Tol)₂ and trimethylamine, give a series of new auracyclic complexes containing the Au–NR–CH₂CH₂–NR (R = SO₂Tol) and Au–NR–C₆H₄–NR (R = COMe or SO₂Tol) five-membered ring systems. An X-ray structure determination on (2-bp)Au{N(COMe)C₆H₄N(COMe)} (2-bp = cycloaurated 2-benzylpyridine) shows the presence of puckered metallacyclic rings, with both acetyl substituents positioned below the Au(III) coordination plane. The complex (2-bp)Au{N(COMe)C₆H₄N(COMe)} undergoes ring cleavage in the presence of halide and water, to give the complex (2-bp)Au{N(COMe)C₆H₄NH(COMe)}Cl, which was characterised crystallographically, and shown to contain a monodentate amidate ligand. Biological activity studies of the new auracyclic complexes are also reported, against P388 murine leukaemia cells and a range of bacteria and fungi, with a number of complexes showing high activity.     

Hexacyanometallate anions as precursors of two new trinuclear heterobimetallic assemblies: Syntheses,structures and cryomagnetic properties

Two new cyano bridged Cu–Co and Cu–Fe trinuclear bimetallic assemblies, [(CuL)[Co(CN)₆](CuL)]ClO₄ · 3.5H₂O (1) and [(CuL)[Fe(CN)₆](CuL)] · 13H₂O (2) where [L = (3E,5E)-N¹,N⁴-bis((pyridin-2-yl)methylene)butane-1,4-diamine] have been prepared using cyanometallates as anion precursors and characterised by elemental analyses, spectroscopic studies, single crystal X-ray diffraction and cryomagnetic susceptibility measurements. Magneto-structural correlations have been drawn from cryomagnetic susceptibility measurements over a wide temperature range (2–300 K) under 0.5 T magnetic fields. Weak antiferromagnetic interactions with J = −0.81 and −0.73 cm⁻¹ are found for 1 and 2, respectively, showing a very weak coupling, as expected from the diamagnetic long chain –NC–Co–CN–CN– and –NC–Fe–CN–CN– bridges revealed from the single crystal X-ray diffraction studies.     

Stabilisation of heterobimetallic networks by crown ethers and hydrogen-bonding in [Ni(H2O)6][Cu3Cl8(H2O)2] · (15-crown-5)2 · 2H2O: Structure and magnetism

[Ni(H₂O)₆][Cu₃Cl₈(H₂O)₂] · (15-crown-5)₂ · 2H₂O can be conveniently prepared by the interaction of NiCl₂ · 6H₂O, CuCl₂ · 2H₂O and 15-crown-5 in water. The X-ray crystal structure reveals an ionic complex involved in a hydrogen-bonded two dimensional network with the [Ni(H₂O)₆]²⁺ and [Cu₃Cl₈(H₂O)₂]²⁻ ions sandwiched between the 15-crown-5 macrocycles. The magnetic susceptibility data (4–300 K) and magnetisation isotherms (2–5.5 K; 0–5 T) are best interpreted in terms of intra-trimer ferromagnetic coupling within the [Cu₃Cl₈(H₂O)₂]²⁻ moieties, with J ∼ 6 cm⁻¹, and antiferromagnetic coupling between the trimers, the latter mediated by H-bonding pathways. Comparisons are made to other reported quaternary ammonium salts of [Cu₃Cl₈]²⁻ and [Cu₃Cl₁₂]⁶⁻, most of which display structures that involve close stacking of such Cu(II) trimers, rather than being of the present isolated, albeit H-bonded, types.     

Thin Pd–23%Ag/stainless steel composite membranes: Long-term stability,life-time estimation and post-process characterisation

The long-term stability of Pd–23%Ag/stainless steel composite membranes has been examined in H₂/N₂ mixtures as a function of both temperature and feed pressure. During continuous operation, the membrane shows a good stability at 400 °C while the N₂ leakage increases very slowly at a temperature of 450 °C (P_feed = 10 bar). After 100 days of operation (P_feed = 5–20 bar, T = 350–450 °C), the N₂ permeance equals 7.0 × 10⁻⁹ mol m⁻² s⁻¹ Pa⁻¹, which indicates that the H₂/N₂ permselectivity still lies around 500, based on a H₂ permeance equal to 3.0 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹. Despite the generation of small pinholes, a membrane life-time of several (2–3) years (T ≤ 425 °C) is estimated for the experimental conditions employed based on long-term stability tests over 100 days. Post-process characterisation shows a considerable grain growth and micro-strain relaxation in the Pd–23%Ag membrane after the prolonged permeation experiment. Changes in surface area are relatively small. In addition, segregation of Ag to the membrane surfaces is observed. The formation of pinholes is identified as the main source for the increased N₂ leakage during testing at higher temperature.     

Synthesis,structures and luminescent properties of 4d–4f heterometallic coordination frameworks based on lanthanide oxalate substructures with nicotinate bridging ligands

Four transition–lanthanide metal–organic coordination polymers, namely [Ag₂Ln(nic)₄(H₂O)₄ · (ClO₄) · H₂O] [Ln = Eu (1), Gd (2)] and [AgLn(nic)₂(ox)_0.5(H₂O)₂ · (ClO₄) · H₂O] [Ln = Tb (3), Yb (4)] (nic = nicotinate; ox = oxalate) have been synthesized by the hydrothermal reactions of 4d and 4f metal salts with N-/O-donor ligands. The isostructural complexes 1 and 2 exhibit novel 2D wave-like heterometallic layers constructed by the assembly of 1D chains of lanthanide–carboxylate with Ag(nic)₂ subunits. Complexes 3 and 4 show another unusual 3D heterometallic coordination framework constructed from 2D lanthanide–oxalate layers and pillar-like Ag(nic)₂ subunits. Furthermore, the luminescent properties of complexes 1 and 3 were studied.     

Magnetism and crystal structures of CuMn and CuNi ordered bimetallic chains

The syntheses, crystal structures and magnetic properties of the new bimetallic compounds {CuL_α[Ni(NCS)₄(H₂O)₂]} (1) and {CuL_α[Mn(NCS)₄(H₂O)₂]} (2), where L = N-dl-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene, are reported. Both structures consist of well-separated and magnetically equivalent layers which are composed of thiocyanate-bridged Cu(II)–Mn(II) or Cu(II)–Ni(II) binuclear units and create infinite polymeric zig-zag-like chains in the crystal lattices. The [Ni(NCS)₄(H₂O)₂] and [Mn(NCS)₄(H₂O)₂] molecular fragments have a distorted octahedral symmetry. The geometry of the Cu(II) unit is octahedral with the apical positions occupied by bridging thiocyanate ligands and the basal ones by four nitrogen atoms from the macrocyclic ring. The shortest intramolecular M–M distances are: 6.342 Å (Cu–Ni) and 6.421 Å (Cu–Mn). Magnetic susceptibility and magnetization measurements for the examined compounds have been carried out over the range 1.8–300 K. The data suggest antiferromagnetic interactions through the thiocyanate bridge. Finally, the magnitudes of the Cu(II)–M(II) interactions (M = Ni and Mn) have been compared and qualitatively rationalised.     

Catalytic gold nanoparticles for fluorescent detection of mercury(II) and lead(II) ions

In this study, we developed a fluorescence assay for the highly sensitive and selective detection of Hg²⁺ and Pb²⁺ ions using a gold nanoparticle (Au NP)-based probe. The Hg–Au and Pb–Au alloys that formed on the Au NP surfaces allowed the Au NPs to exhibit peroxidase-mimicking catalytic activity in the H₂O₂-mediated oxidation of Amplex UltraRed (AUR). The fluorescence of the AUR oxidation product increased upon increasing the concentration of either Hg²⁺ or Pb²⁺ ions. By controlling the pH values of 5 mM tris–acetate buffers at 7.0 and 9.0, this H₂O₂–AUR–Au NP probe detected Hg²⁺ and Pb²⁺ ions, respectively, both with limits of detection (signal-to-noise ratio: 3) of 4.0 nM. The fluorescence intensity of the AUR oxidation product was proportional to the concentrations of Hg²⁺ and Pb²⁺ ions over ranges 0.05–1 μM (R² = 0.993) and 0.05–5 μM (R² = 0.996), respectively. The H₂O₂–AUR–Au NP probe was highly selective for Hg²⁺ (>100-fold) and Pb²⁺ (>300-fold) ions in the presence of other tested metal ions. We validated the practicality of this simple, selective, and sensitive H₂O₂–AUR–Au NP probe through determination of the concentrations of Hg²⁺ and Pb²⁺ ions in a lake water sample and of Pb²⁺ ions in a blood sample. To the best of our knowledge, this system is the first example of Au NPs being used as enzyme-mimics for the fluorescence detection of Hg²⁺ and Pb²⁺ ions.     

Conversion of novel palladacycles into oxopyrrolo[3,4-b]quinolines

The quinolinylcyclopalladated complexes 3a–b were synthesised in good yields (81% and 77%) by the insertion reaction of the prepared dinuclear palladium complexes [Pd(C,N-2-C₉H₄N-CHO-3-R-6)Cl(PPh₃)]₂ [(R = H (2a), R = OMe (2b)] with isonitrile XyNC (Xy = 2,6-Me₂C₆H₃). The cyclopalladated complexes 3a–b were also obtained in low yields (39% and 33.5%) via a one pot oxidative addition reaction of quinoline chloride 1a–b with isonitrile XyNC:Pd(dba)₂ (4:1). The reactions of 3a–b with Tl(TfO) (TfO = triflate, CF₃SO₃) in the presence of H₂O or EtOH causes depalladation reactions of the complexes to provide the corresponding organic compounds 4a–b, 5a–b and 6a–b in yields (41%, 27% and 18–19%). The products were characterized by satisfactory elemental analyses and spectral studies (IR, ¹H, ¹³C and ³¹P NMR). The crystal structures of 2a, 3a and 3b were determined by X-ray diffraction studies.     

Solid–liquid phase equilibria in the system K2SO4–MgSO4–H2O at 318 K

The polythermal solubility diagram of the system K₂SO₄–MgSO₄–H₂O presents the formation of three double salts, picromerite, leonite, langbeinite appearing in this order with increasing temperature. In the temperature range between 314.15 K and 320.65 K, picromerite and leonite ought to coexist. The search in the literature revealed a lack of isothermal phase equilibrium data within this temperature range. Therefore, the solubility in the system K₂SO₄–MgSO₄–H₂O was determined in the whole concentration range at 318 K. The solid phases, epsomite, leonite, picromerite and arcanite occur with increasing potassium sulfate concentration. A two-salt point of leonite and picromerite is established at 0.618 molal K₂SO₄ and 3.030 molal MgSO₄ at the temperature of investigation.