Complexes self‐associate by hydrogen bonding and metallophilic attraction: Theoretical study

Hydrogen bonding and metallophilic attractions are studied in the model systems: [(AuNH₃Cl)₂], [(AuNH(CH₃)₂Cl)₂], [{Au₂(μ‐SH)(PH₂O)(PH₂OH)}₂], [(CuNH₃Cl)₂], and [{Cu(NH₃)Cl}₄] at the Hartree–Fock (HF) and second‐order Møller–Plesset (MP2) levels. The two interactions are found to be comparable and prevailing in the final structure. It is determined that the aurophilic contact has a same magnitude that the hydrogen bonding, and is stronger than the cuprophilic interaction. The presence of hydrogen bond directs the growth of the crystal. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Theoretical study of the electronic spectrum of binuclear gold(I) complexes

The electronic structure and the spectroscopic properties of [Au₂(CS₃)₂]^?2, [Au₂(pym‐2‐S)₂] (pym = pyrimidethiolate), [Au₂(dpm)₂]⁺² (dpm = bis(diphosphino)methane) were studied using density functional theory (DFT) at the B3LYP level. The absorption spectrum of these binuclear gold(I) complexes was calculated by single excitation time‐dependent (TD) method. All complexes showed a ¹(5dσ* → 6pσ) transition associated with a metal–metal charge transfer, which is strongly interrelated with the gold–gold distance. Furthermore, we have calculated the frequency of the gold–gold vibration (ν_Au2) on the above complexes. The values obtained are theoretically in agreement with experimental range. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

High-performance liquid chromatographic determination of naltrexone in plasma of hemodialysis patients

A simple, sensitive, selective and reliable reversed-phase high-performance liquid chromatographic (HPLC) method with UV detection is described for the determination of naltrexone in plasma samples. Naltrexone and the internal standard, naloxone, were isolated from plasma either with a liquid-liquid extraction method using ethyl acetate or with a solid-phase extraction method using Sep-Pack C18 cartridge before chromatography. The extracts were dried under a stream of nitrogen and the samples were reconstituted in the mobile phase, then 20 microL were injected on a Waters Symmetry C18 column (5 microm particle size, 4.6 x 150 mm). The mobile phase consisted of 0.06% triethylamine (pH 2.8)-acetonitrile (92:8, v/v) pumped at 1 mL/min. The peak-area ratio versus plasma concentration was linear over the range of 10-500 ng/mL and the detection limit was less than 8 ng/mL. Quantification was by ultra-violet detection at 204 nm. The present method was applied to the determination of the plasma concentration of naltrexone in dialyzed patients. Patients (n = 8) with severe generalized pruritus received 50 mg of naltrexone orally per day for 2 weeks. The variability in the therapeutic response in treated patients required plasma concentration investigations of this opioid antagonist.     

Octanuclear and nonanuclear supramolecular copper(II) complexes with linear "tritopic" ligands: structural and magnetic studies

The structures and magnetic properties of self-assembled copper(II) clusters and grids with the "tritopic" ligands 2poap (a), Cl2poap (b), m2poap (c), Cl2pomp (d), and 2pomp (e) are described [ligands derived by reaction of 4-R-2,6-pyridinedicarboxylic hydrazide (R = H, Cl, MeO) with 2-pyridinemethylimidate (a-c, respectively) or 2-acetylpyridine (d, R = Cl; e, R = H)]. Cl2poap and Cl2pomp self-assemble with Cu(NO(3))(2) to form octanuclear "pinwheel" cluster complexes [Cu(8)(Cl2poap-2H)(4)(NO(3))(8)].20H(2)O (1) and [Cu(8)(Cl2pomp-2H)(4)(NO(3))(8)].15H(2)O (2), built on a square [2 x 2] grid with four pendant copper arms, using "mild" reaction conditions. Similar reactions of Cl2pomp and 2pomp with Cu(ClO(4))(2) produce pinwheel clusters [Cu(8)(Cl2pomp-2H)(4)(H(2)O)(8)](ClO(4))(8).7H(2)O (3) and [Cu(8)(2pomp-2H)(4)(H(2)O)(8)](ClO(4))(8) (4), respectively. Heating a solution of 1 in MeOH/H(2)O produces a [3 x 3] nonanuclear square grid complex, [Cu(9)(Cl2poap-H)(3)(Cl2poap-2H)(3)](NO(3))(9).18H(2)O (5), which is also produced by direct reaction of the ligand and metal salt under similar conditions. Reaction of m2poap with Cu(NO(3))(2) produces only the [3 x 3] grid [Cu(9)(m2poap-H)(2)(m2poap-2H)(4)](NO(3))(8).17H(2)O (6) under similar conditions. Mixing the tritopic ligand 2poap with pyridine-2,6-dicarboxylic acid (picd) in the presence of Cu(NO(3))(2) produces a remarkable mixed ligand, nonanuclear grid complex [Cu(9)(2poap-H)(4)(picd-H)(3)(picd-2H)](NO(3))(9).9H(2)O (7), in which aromatic pi-stacking interactions are important in stabilizing the structure. Complexes 1-3 and 5-7 involve single oxygen atom (alkoxide) bridging connections between adjacent copper centers, while complex 4 has an unprecedented mixed micro-(N-N) and micro-O metal ion connectivity. Compound 1 (C(76)H(92)N(44)Cu(8)O(50)Cl(4)) crystallizes in the tetragonal system, space group I, with a = 21.645(1) A, c = 12.950(1) A, and Z = 2. Compound 2 (C(84)H(88)N(36)O(44)Cl(4)Cu(8)) crystallizes in the tetragonal system, space group I, with a = 21.2562(8) A, c = 12.7583(9) A, and Z = 2. Compound 4 (C(84)H(120)N(28)O(66)Cl(8)Cu(8)) crystallizes in the tetragonal system, space group I4(1)/a, with a = 20.7790(4) A, c = 32.561(1) A, and Z = 4. Compound 7(C(104)H(104)N(46)O(56)Cu(9)) crystallizes in the triclinic system, space group P, with a = 15.473(1) A, b = 19.869(2) A, c = 23.083(2) A, alpha = 88.890(2) degrees, beta = 81.511(2) degrees, gamma = 68.607(1) degrees, and Z = 2. All complexes exhibit dominant intramolecular ferromagnetic exchange coupling, resulting from an orthogonal bridging arrangement within each polynuclear structure.     

Metallomacrocycle (MacM) complex with cyanide as bridged ligand: Electronic structures of [MacMCN]n

The electronic structures of complexes and one‐dimensional metallomacrocycles with cyanide as bridged ligand, such as [MacM(CN)₂]^? and [MacM(CN)]_n [Mac=phthalocyanine, tetrabenzoporphyrine; M=Co(III), Rh(III)] have been investigated using density functional theory. The results of this study show that the intrinsic semiconductivity properties depend on the frontier bands. The valence band is composed by the π‐macrocycle orbital. The conduction band for the cobalt polymers is a mixture of orbitals between this metal and the cyanide ligand along of the stacking direction. However, in the rhodium polymers such a band is exclusively composed of the π* system of the macrocycles. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem, 2002     

Biocompatible hydrogels based on chitosan,cellulose/starch,PVA and PEDOT:PSS with high flexibility and high mechanical strength

Fabricating mechanically strong hydrogels that can withstand the conditions in internal tissues is a challenging task. We have designed hydrogels based on multicomponent systems by combining chitosan, starch/cellulose, PVA, and PEDOT:PSS via one-pot synthesis. The starch-based hydrogels were homogeneous, while the cellulose-based hydrogels showed the presence of cellulose micro- and nanofibers. The cellulose-based hydrogels demonstrated a swelling ratio between 121 and 156%, while the starch-based hydrogels showed higher values, from 234 to 280%. Tensile tests indicated that the presence of starch in the hydrogels provided high flexibility (strain at break?>?300%), while combination with cellulose led to the formation of stiffer hydrogels (elastic moduli 3.9–6.6 MPa). The ultimate tensile strength for both types of hydrogels was similar (2.8–3.9 MPa). The adhesion and growth of human osteoblast-like SAOS-2 cells was higher on hydrogels with cellulose than on hydrogels with starch, and was higher on hydrogels with PEDOT:PSS than on hydrogels without this polymer. The metabolic activity of cells cultivated for 3 days in the hydrogel infusions indicated that no acutely toxic compounds were released. This is promising for further possible applications of these hydrogels in tissue engineering or in wound dressings.

Graphical abstract

     

Harnack’s inequality for a class of non-divergent equations in the Heisenberg group

We prove an invariant Harnack’s inequality for operators in non-divergence form structured on Heisenberg vector fields when the coe?cient matrix is uniformly positive definite, continuous, and symplectic. The method consists in constructing appropriate barriers to obtain pointwise-to-measure estimates for supersolutions in small balls, and then invoking the axiomatic approach developed by Di Fazio, Gutiérrez, and Lanconelli to obtain Harnack’s inequality.     

Oxotitanium(IV) complexes of some bis‐unsymmetric Schiff bases: Synthesis,structural elucidation and biomedical applications

A number of oxotitanium(IV) complexes of the type TiOL with bis‐unsymmetric dibasic tetradentate Schiff base (LH₂) containing ONNO donor atoms have been synthesized. Mono‐Schiff base (OPD‐HNP) was prepared by the condensation of 1:3 molar ratio of 2‐hydroxy‐1‐naphthaldehyde (HNP) with o‐phenylenediamine (OPD). Dibasic unsymmetric tetradentate diamine Schiff bases were prepared by the reaction of OPD‐HNP with 2‐hydroxyacetophenone, 2‐hydroxypropeophenone, benzoylacetone, acetylacetone and ethylacetoacetate. Further, titanylacetylacetonate was reacted with these ligands to obtain their metal complexes. On the basis of analytical and physiochemical data, the formation of complexes as TiOL was suggested having square pyramidal geometry. Quantum mechanical approach also confirmed this geometry. The assessment of the synthesized ligands and their complexes showed that some behave as good inhibitors of mycelial growth against selected phytopathogic fungi but weak inhibitors against some selected bacteria. A few of them also showed antioxidant properties.     

Electrochemical behavior of aluminum and some of its alloys in chloroaluminate ionic liquids: electrolytic extraction and electrorefining

The electrochemical behaviors of pure Al, Al–6%Si, Al–3%Cu, and Al–3.7%Cu–0.9%Mg–0.8%Pb–0.6%Fe alloys were investigated in the chloroaluminate ionic liquids 1-butyl-3-methylimidazolium chloride [BMIm]Cl/AlCl₃ (40/60 mol%) and 1-ethyl-3-methylimidazolium chloride [EMIm]Cl/AlCl₃ (40/60 mol%). Electrolytic extraction of copper from Al–Cu alloys in the employed ionic liquids was explored. The alloys were anodically dissolved in the ionic liquids and then pure copper was recovered under potentiostatic conditions. Due to the large difference between the deposition potentials of Cu and Al, pure Cu can be obtained without Al contamination. Electrorefining of Al–3%Cu and Al–6%Si alloys was also investigated in [BMIm]Cl/AlCl₃ (40/60 mol%) at room temperature. High purity aluminum deposits were obtained with significantly low energy consumption of about 2 kWh/kg of Al.     

Molybdatophosphoric Acid/NaNO2/Wet SiO2 as an Efficient System for the Aromatization of 1,2‐Dihydroquinolines under Mild and Heterogeneous Conditions

A combination of molybdatophosphoric acid and NaNO₂ in the presence of wet SiO₂ was used as an effective oxidizing agent for the oxidation of 1,2‐dihydroquinolines to their corresponding quinoline derivatives in dichlomethane at room temperature with excellent yields.