Synthesis,Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles

The neutral dinuclear complexes [(η⁵-C₅Me₅)₂Rh₂(μ-dhnq)Cl₂] (1) and [(η⁵-C₅Me₅)₂Ir₂(μ-dhnq)Cl₂] (2) (dhnqH₂ = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂ (M = Rh, Ir) with dhnqH₂ in the presence of CH₃COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF₃SO₃, affords the corresponding tetranuclear metalla-rectangles [(η⁵-C₅Me₅)₄M₄(μ-dhnq)₂(μ-L)₂]⁴⁺ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by infrared, ¹H and ¹³C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC₅₀ values in the low micromolar range.     

Synthesis,Crystal Structure and Luminescent Property of Mg(II) Complex with N-Benzenesulphonyl-L-Leucine and 1,10-Phenanthroline

A new complex [Mg(L)₂(phen)(H₂O)₂](phen)(H₂O)₂ [L= N-benzenesulphonyl-L-leucine] was synthesized by the reaction of magnesium chloride hexahydrate with N-benzenesulphonyl-L-leucine and 1,10-phenanthroline in the CH₃CH₂OH/H₂O (v:v = 5:1). It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The crystal of the title complex [Mg(L)₂(phen)(H₂O)₂](phen)(H₂O)₂ belongs to triclinic, space group P-1 with a = 0.72772(15) nm, b = 1.4279(3) nm, c = 1.4418(3) nm, α = 63.53(3)°, β = 79.75(3)°, γ = 81.83(3)°, V = 1.3163(5) nm³, Z =1, D_c= 1.258 μg·m⁻³, μ = 0.177 mm⁻¹, F(000) = 526, and final R₁ = 0.0506, ωR₂ = 0.1328. The complex comprises a six-coordinated magnesium(II) center, with a N₂O₄ distorted octahedron coordination environment. The molecules are connected by hydrogen bonds and π-π stacking to form one dimensional chain structure. The luminescent property of the Mg(II) complex has been investigated in solid.     

Synthesis,Crystal Structure and Luminescent Property of Cd (II) Complex with N-Benzenesulphonyl-L-leucine

A new trinuclear Cd (II) complex [Cd₃(L)₆(2,2-bipyridine)₃] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P2₁2₁2₁ with a = 16.877(3) Å, b = 22.875(5) Å, c = 29.495(6) Å, α = β = γ = 90°, V = 11387(4) ų, Z = 4, D_c= 1.416 μg·m⁻³, μ = 0.737 mm⁻¹, F (000) = 4992, and final R₁ = 0.0390, ωR₂ = 0.0989. The complex comprises two seven-coordinated Cd (II) atoms, with a N₂O₅ distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II) atom, with a N₂O₄ distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and π-π interaction of 2,2-bipyridine. The luminescent properties of the Cd (II) complex and N-Benzenesulphonyl-L-leucine in solid and in CH₃OH solution also have been investigated.     

A synthetic precedent for the [FeIV2(mu-O)2] diamond core proposed for methane monooxygenase intermediate Q

Intermediate Q, the methane-oxidizing species of soluble methane monooxygenase, is proposed to have an [Fe^IV₂(μ-O)₂] diamond core. In an effort to obtain a synthetic precedent for such a core, bulk electrolysis at 900 mV (versus Fc^+/0) has been performed in MeCN at −40°C on a valence-delocalized [Fe^IIIFe^IV(μ-O)₂(L^b)₂]³⁺ complex (1b) (E_1/2 = 760 mV versus Fc^+/0). Oxidation of 1b results in the near-quantitative formation of a deep red complex, designated 2b, that exhibits a visible spectrum with λ_max at 485 nm (9,800 M⁻¹·cm⁻¹) and 875 nm (2,200 M⁻¹·cm⁻¹). The 4.2 K Mössbauer spectrum of 2b exhibits a quadrupole doublet with δ = −0.04(1) mm·s⁻¹ and ΔE_Q = 2.09(2) mm·s⁻¹, parameters typical of an iron(IV) center. The Mössbauer patterns observed in strong applied fields show that 2b is an antiferromagnetically coupled diiron(IV) center. Resonance Raman studies reveal the diagnostic vibration mode of the [Fe₂(μ-O)₂] core at 674 cm⁻¹, downshifting 30 cm⁻¹ upon ¹⁸O labeling. Extended x-ray absorption fine structure (EXAFS) analysis shows two O/N scatterers at 1.78 Å and an Fe scatterer at 2.73 Å. Based on the accumulated spectroscopic evidence, 2b thus can be formulated as [Fe^IV₂(μ-O)₂(L^b)₂]⁴⁺, the first synthetic complex with an [Fe^IV₂(μ-O)₂] core. A comparison of 2b and its mononuclear analog [Fe^IV(O)(L^b)(NCMe)]²⁺ (4b) reveals that 4b is 100-fold more reactive than 2b in oxidizing weak CH bonds. This surprising observation may shed further light on how intermediate Q carries out the hydroxylation of methane.     

Relevance of the reaction of a manganese(III) chelate with hydroxide ion to photosynthesis: Reaction of hydroxide ion with 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphinatomanganese(III) in ligating and nonligating solvents

The reaction of HO^- with 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)porphinatomanganese(III) chloride [(TMP)Mn^III(Cl)] in ligating solvents (CH₃CN, dimethyl sulfoxide, pyridine) results in formation of (TMP)Mn^II (≈10⁶ M^-1·s^-r), which in a slower reaction is converted to a product whose structure is suggested to be that of a porphyrin manganese(III) peroxo dimer. Admittance of O₂ at any time during these reactions leads to formation of the manganese(III) peroxide (TMP)Mn^III(O₂)^-. In nonligating solvents [CH₂Cl₂, (CH₃)₂CO], the reaction of HO^- with (TMP)Mn^III(Cl) yields (TMP)Mn^IV(OH)₂.     

Molecular and Polymer Ln2M2 (Ln = Eu,Gd, Tb,Dy; M = Zn,Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties

Varying the temperature of the reaction of [{Cd(pfb)(H₂O)₄}⁺_n·n(pfb)⁻], [Ln₂(pfb)₆(H₂O)₈]·H₂O (Hpfb = pentafluorobenzoic acid), and 1,10-phenanthroline (phen) in MeCN followed by crystallization resulted in the isolation of two type of products: 1D-polymers [LnCd(pfb)₅(phen)]_n·1.5nMeCN (Ln = Eu (I), Gd (II), Tb (III), Dy (IV)) which were isolated at 25 °C, and molecular compounds [Tb₂Cd₂(pfb)₁₀(phen)₂] (V) formed at 75 °C. The transition from a molecular to a polymer structure becomes possible because of intra- and intermolecular interactions between the aromatic cycles of phen and pfb from neighboring tetranuclear Ln₂Cd₂ fragments. Replacement of cadmium with zinc in the reaction resulted in molecular compounds Ln₂Zn₂ [Ln₂Zn₂(pfb)₁₀(phen)₂]·4MeCN (Ln = Eu (VI), Tb (VIII), Dy (IX)) and [Gd₂Zn₂(pfb)₁₀(H₂O)₂(phen)₂]·4MeCN (VII). A new molecular EuCd complex [Eu₂Cd₂(pfb)₁₀(phen)₄]·4MeCN (X)] was isolated from a mixture of cadmium, zinc, and europium pentafluorobenzoates (Cd:Zn:Ln = 1:1:2). Complexes II-IV, VII and IX exhibit magnetic relaxation at liquid helium temperatures in nonzero magnetic fields. Luminescent studies revealed a bright luminescence of complexes with europium(III) and terbium(III) ions.     

Crystal Structure,Spectroscopic Characterization,Antioxidant and Cytotoxic Activity of New Mg(II) and Mn(II)/Na(I) Complexes of Isoferulic Acid

The Mg(II) and heterometallic Mn(II)/Na(I) complexes of isoferulic acid (3-hydroxy-4-methoxycinnamic acid, IFA) were synthesized and characterized by infrared spectroscopy FT-IR, FT-Raman, electronic absorption spectroscopy UV/VIS, and single-crystal X-ray diffraction. The reaction of MgCl₂ with isoferulic acid in the aqueous solutions of NaOH resulted in synthesis of the complex salt of the general formula of [Mg(H₂O)₆]⋅(C₁₀H₉O₄)₂⋅6H₂O. The crystal structure of this compound consists of discrete octahedral [Mg(H₂O)₆]²⁺ cations, isoferulic acid anions and solvent water molecules. The hydrated metal cations are arranged among the organic layers. The multiple hydrogen-bonding interactions established between the coordinated and lattice water molecules and the functional groups of the ligand stabilize the 3D architecture of the crystal. The use of MnCl₂ instead of MgCl₂ led to the formation of the Mn(II)/Na(I) complex of the general formula [Mn₃Na₂(C₁₀H₇O₄)₈(H₂O)₈]. The compound is a 3D coordination polymer composed of centrosymmetric pentanuclear subunits. The antioxidant activity of these compounds was evaluated by assays based on different antioxidant mechanisms of action, i.e., with ^•OH, DPPH^• and ABTS^•+ radicals as well as CUPRAC (cupric ions reducing power) and lipid peroxidation inhibition assays. The pro-oxidant property of compounds was measured as the rate of oxidation of Trolox. The Mg(II) and Mn(II)/Na(I) complexes with isoferulic acid showed higher antioxidant activity than ligand alone in DPPH (IFA, IC₅₀ = 365.27 μM, Mg(II) IFA IC₅₀ = 153.50 μM, Mn(II)/Na(I) IFA IC₅₀ = 149.00 μM) and CUPRAC assays (IFA 40.92 μM of Trolox, Mg(II) IFA 87.93 μM and Mn(II)/Na(I) IFA 105.85 μM of Trolox; for compounds’ concentration 10 μM). Mg(II) IFA is a better scavenger of ^•OH than IFA and Mn(II)/Na(I) IFA complex. There was no distinct difference in ABTS^•+ and lipid peroxidation assays between isoferulic acid and its Mg(II) complex, while Mn(II)/Na(I) complex showed lower activity than these compounds. The tested complexes displayed only slight antiproliferative activity tested in HaCaT human immortalized keratinocyte cell line within the solubility range. The Mn(II)/Na(I) IFA (16 μM in medium) caused an 87% (±5%) decrease in cell viability, the Mg salt caused a comparable, i.e., 87% (±4%) viability decrease in a concentration of 45 μM, while IFA caused this level of cell activity attenuation (87% ± 5%) at the concentration of 1582 μM (significant at α = 0.05).     

Effect of Heating Modes on Reactive Sintering of Ca3Co4O9 Ceramics

The traditional solid-state reaction method was employed to synthesize bulk calcium cobaltite (Ca349/Ca₃Co₄O₉) ceramics via ball milling the precursor mixture. The samples were compacted using conventional sintering (CS) and spark plasma sintering (SPS) at 850, 900, and 950 °C. The X-ray diffraction (XRD) pattern indicates the presence of the Ca349 phase for samples sintered at 850 and 900 °C. In addition, SPS fosters higher densification (81.18%) than conventional sintering (50.76%) at elevated sintering temperatures. The thermo-gravimetric analysis (TGA) and differential thermal analysis (DTA) performed on the precursor mixture reported a weight loss of ~25.23% at a temperature range of 600–820 °C. This current work aims to analyze the electrical properties (Seebeck coefficient (s), electrical resistivity (ρ), and power factor) of sintered samples as a function of temperature (35–500 °C). It demonstrates that the change in sintering temperature (conventional sintering) did not evince any significant change in the Seebeck coefficient (113–142 μV/K). However, it reported a low resistivity of 153–132 μΩ-m and a better power factor (82–146.4 μW/mK²) at 900 °C. On the contrary, the SPS sintered samples recorded a higher Seebeck coefficient of 121–181 μV/K at 900 °C. Correspondingly, the samples sintered at 950 °C delineated a low resistivity of 145–158 μΩ-m and a better power factor (97–152 μW/mK²).     

Reversible Redox Property of Co(III) in Amorphous Co-Doped SiO2/γ-Al2O3 Layered Composites

This paper reports on a unique reversible reducing and oxidizing (redox) property of Co(III) in Co-doped amorphous SiO₂/γ-Al₂O₃ composites. The Fenton reaction during the H₂O₂-catalyzed sol–gel synthesis utilized in this study lead to the partial formation of Co(III) in addition to Co(II) within the composites. High-resolution transmission electron microscopy (HRTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) analyses for the composite powder sample with a composition of Al:Si:Co = 85:10:5 showed the amorphous state of the Co-doped SiO₂ that modified γ-Al₂O₃ nanocrystalline surfaces. In situ X-ray absorption fine structure (XAFS) spectroscopic analysis suggested reversible redox reactions of Co species in the composite powder sample during heat-treatment under H₂ at 500 °C followed by subsequent cooling to RT under Ar. Further analyses by in situ IR spectroscopy combined with cyclic temperature programmed reduction/desorption (TPR/TPD) measurements and X-ray photoelectron spectroscopic (XPS) analysis revealed that the alternating Co(III)/(II) redox reactions were associated with OH formation (hydrogenation)-deformation (dehydrogenation) of the amorphous aluminosilicate matrix formed in situ at the SiO₂/γ-Al₂O₃ hetero interface, and the redox reactions were governed by the H₂ partial pressure at 250–500 °C. As a result, a supported mesoporous γ-Al₂O₃/Co-doped amorphous SiO₂/mesoporous γ-Al₂O₃ three-layered composite membrane exhibited an H₂-triggered chemical valve property: mesopores under H₂ flow (open) and micropores under He flow (closure) at 300–500 °C.     

Accelerating slow excited state proton transfer

Visible light excitation of the ligand-bridged assembly [(bpy)₂Ru_a^II(L)Ru_b^II(bpy)(OH₂)⁴⁺] (bpy is 2,2′-bipyridine; L is the bridging ligand, 4-phen-tpy) results in emission from the lowest energy, bridge-based metal-to-ligand charge transfer excited state (L^−•)Ru_b^III-OH₂ with an excited-state lifetime of 13 ± 1 ns. Near–diffusion-controlled quenching of the emission occurs with added HPO₄²⁻ and partial quenching by added acetate anion (OAc⁻) in buffered solutions with pH control. A Stern–Volmer analysis of quenching by OAc⁻ gave a quenching rate constant of k_q = 4.1 × 10⁸ M⁻¹⋅s⁻¹ and an estimated pK_a* value of ∼5 ± 1 for the [(bpy)₂Ru_a^II(L^•−)Ru_b^III(bpy)(OH₂)⁴⁺]* excited state. Following proton loss and rapid excited-state decay to give [(bpy)₂Ru_a^II(L)Ru_b^II(bpy)(OH)³⁺] in a H₂PO₄⁻/HPO₄²⁻ buffer, back proton transfer occurs from H₂PO₄⁻ to give [(bpy)₂Ru_a^II(L)Ru_b(bpy)(OH₂)⁴⁺] with k_PT,2 = 4.4 × 10⁸ M⁻¹⋅s⁻¹. From the intercept of a plot of k_obs vs. [H₂PO₄⁻], k = 2.1 × 10⁶ s⁻¹ for reprotonation by water providing a dramatic illustration of kinetically limiting, slow proton transfer for acids and bases with pK_a values intermediate between pK_a(H₃O⁺) = −1.74 and pK_a(H₂O) = 15.7.     

Dendritic Iron(III) Carbazole Complexes: Structural,Optical, and Magnetic Characteristics

This paper focuses on the synthesis, structural characterization, and study of the optical, magnetic, and thermal properties of novel architectures combining metal ions as magnetoactive centers and photoactive blocks formed by carbazole units. For this purpose, a series of azomethine complexes of the composition [Fe(L)₂]X (L = 3,6-bis[(3′,6′-di-tert-butyl-9-carbazol)-9-carbazol]benzoyloxy-4-salicylidene-N′-ethyl-N-ethylenediamine, X = NO₃⁻, Cl⁻, PF₆⁻) were synthesized by the reaction of metal salts with Schiff bases in a mixture of solvents. The UV–Vis absorption properties were studied in dichloromethane and rationalized via time-dependent density functional theory (DFT) calculations. Upon excitation at 350 nm, the compounds exhibited an intense dual fluorescence with two emission bands centered at ~445 and ~485 nm, which were assigned to π_carb–π* intraligand and π_carb–d_Fe ligand-to-metal charge-transfer excited states. EPR spectroscopy and SQUID magnetometry revealed solid-state partial spin crossover in some compounds, and antiferromagnetic interactions between the neighboring Fe(III) ions.     

Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites

Structural characterization of the catalytically significant sites on solid catalyst surfaces is frequently tenuous because their fraction, among all sites, typically is quite low. Here we report the combined application of solid-state ¹³C-cross-polarization magic angle spinning nuclear magnetic resonance (¹³C-CPMAS-NMR) spectroscopy, density functional theory (DFT), and Zr X-ray absorption spectroscopy (XAS) to characterize the adsorption products and surface chemistry of the precatalysts (η⁵-C₅H₅)₂ZrR₂ (R = H, CH₃) and [η⁵-C₅(CH₃)₅]Zr(CH₃)₃ adsorbed on Brønsted superacidic sulfated alumina (AlS). The latter complex is exceptionally active for benzene hydrogenation, with ∼100% of the Zr sites catalytically significant as determined by kinetic poisoning experiments. The ¹³C-CPMAS-NMR, DFT, and XAS data indicate formation of organozirconium cations having a largely electrostatic [η⁵-C₅(CH₃)₅]Zr(CH₃)₂⁺···AlS⁻ interaction with greatly elongated Zr···O_AlS distances of ∼2.35(2) Å. The catalytic benzene hydrogenation cycle is stepwise understandable by DFT, and proceeds via turnover-limiting H₂ delivery to surface [η⁵-C₅(CH₃)₅]ZrH₂(benzene)⁺···AlS⁻ species, observable by solid-state NMR and XAS.     

Insights into the P-to-Q conversion in the catalytic cycle of methane monooxygenase from a synthetic model system

For the catalytic cycle of soluble methane monooxygenase (sMMO), it has been proposed that cleavage of the O–O bond in the (μ-peroxo)diiron(III) intermediate P gives rise to the diiron(IV) intermediate Q with an Fe₂(μ–O)₂ diamond core, which oxidizes methane to methanol. As a model for this conversion, (μ–oxo) diiron(III) complex 1 ([Fe^III₂(μ–O)(μ–O₂H₃)(L)₂]³⁺, L = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) has been treated consecutively with one eq of H₂O₂ and one eq of HClO₄ to form 3 ([Fe^IV₂(μ–O)₂(L)₂]⁴⁺). In the course of this reaction a new species, 2, can be observed before the protonation step; 2 gives rise to a cationic peak cluster by ESI-MS at m/z 1,399, corresponding to the {[Fe₂O₃L₂H](OTf)₂}⁺ ion in which 1 oxygen atom derives from 1 and the other two originate from H₂O₂. Mössbauer studies of 2 reveal the presence of two distinct, exchange coupled iron(IV) centers, and EXAFS fits indicate a short Fe–O bond at 1.66 Å and an Fe–Fe distance of 3.32 Å. Taken together, the spectroscopic data point to an HO-Fe^IV-O-Fe^IV = O core for 2. Protonation of 2 results in the loss of H₂O and the formation of 3. Isotope labeling experiments show that the [Fe^IV₂(μ–O)₂] core of 3 can incorporate both oxygen atoms from H₂O₂. The reactions described here serve as the only biomimetic precedent for the conversion of intermediates P to Q in the sMMO reaction cycle and shed light on how a peroxodiiron(III) unit can transform into an [Fe^IV₂(μ–O)₂] core.     

Humidity-Sensing Properties of an 1D Antiferromagnetic Oxalate-Bridged Coordination Polymer of Iron(III) and Its Temperature-Induced Structural Flexibility

A novel one-dimensional (1D) oxalate-bridged coordination polymer of iron(III), {[NH(CH₃)(C₂H₅)₂][FeCl₂(C₂O₄)]}_n (1), exhibits remarkable humidity-sensing properties and very high proton conductivity at room temperature (2.70 × 10⁻⁴ (Ω·cm)⁻¹ at 298 K under 93% relative humidity), in addition to the independent antiferromagnetic spin chains of iron(III) ions bridged by oxalate groups (J = −7.58(9) cm⁻¹). Moreover, the time-dependent measurements show that 1 could maintain a stable proton conductivity for at least 12 h. Charge transport and magnetic properties were investigated by impedance spectroscopy and magnetization measurements, respectively. Compound 1 consists of infinite anionic zig-zag chains [FeCl₂(C₂O₄)]_nⁿ⁻ and interposed diethylmethylammonium cations (C₂H₅)₂(CH₃)NH⁺, which act as hydrogen bond donors toward carbonyl oxygen atoms. Extraordinarily, the studied coordination polymer exhibits two reversible phase transitions: from the high-temperature phase HT to the mid-temperature phase MT at T ~213 K and from the mid-temperature phase MT to the low-temperature phase LT at T ~120 K, as revealed by in situ powder and single-crystal X-ray diffraction. All three polymorphs show large linear thermal expansion coefficients.     

Effects of non-steroidal anti-inflammatory drugs and prostaglandins on alkali secretion by rabbit gastric fundus in vitro

The effects of non-steroidal anti-inflammatory drugs and prostaglandins E₂ and F_2α on the secretory and electrical activity of isolated rabbit fundic mucosa have been studied. Spontaneous acid secretion was inhibited by serosal side application of sodium thiocyanate (6×10⁻²M) and the resulting alkali secretion measured by pH stat tiration. Serosal side application of indomethacin (10⁻⁵M) or aspirin (3×10⁻³M) inhibited alkali secretion (0·55±0·06 to 0·12±0·06 μmol/cm²/h, n=6, p<0·01 and 0·28±0·06 to 0·11±0·03 μmol/cm²/h, n=7, p<0·02 respectively). Mucosal or serosal side prostaglandin E₂ (10⁻⁵ to 10⁻¹⁰M) and F_2α (10⁻⁴ to 10⁻¹⁰M) failed to alter the rate of alkalinisation but secretion was significantly increased by serosal side 16,16-dimethyl-prostaglandin E₂ (10⁻⁶M) (0·90±0·20 to 1·50±0·30 μmol/cm²/h, n=6, p<0·01). Serosal side application of 10⁻⁶M prostaglandin E₂ to fundic mucosae pretreated with either aspirin (5×10⁻³M) or indomethacin (10⁻⁵M), to reduce endogenous E₂ formation, also failed to alter alkali secretion. Pretreatment of the mucosa with 16,16-dimethyl-E₂ (10⁻⁶M) abolished the inhibitory effect of indomethacin (10⁻⁵M) on alkali secretion (n=6) but did not modify the secretory response to aspirin (3×10⁻³M) (fall in alkali secretion with aspirin = 81±11% and with aspirin plus 16,16-dimethyl-E₂ = 72±10%, n=7). In the doses used, none of the prostaglandins or non-steroidal anti-inflammatory drugs altered transmucosal potential difference or electrical resistance. These results show that the damaging agents, aspirin and indomethacin, both inhibit gastric alkali secretion but that modes of action may differ. The observation that prostaglandins, E₂ and F_2α failed to increase alkali production suggests that their protective activity against a variety of damaging agents as shown by others, may be mediated by another mechanism.     

Nonlinear Optical Properties of Porphyrin,Fullerene and Ferrocene Hybrid Materials

In this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by meso-tetraphenylporphyrin P (both as free base and Zn^II complex), carrying in 2 or 2,12 β-pyrrolic position an electron donor ferrocene (Fc), and/or an electron acceptor fullerene (C60) moiety, connected to the porphyrin core via an ethynyl or an ethynylphenyl spacer. We measured the NLO response by the electric-field-induced second-harmonic generation (EFISH) technique in CH₂Cl₂ solution with a 1907 nm incident wavelength, recording for all the investigated compounds unexpected negative values of μβ₁₉₀₇. Since density functional theory (DFT) calculations evidenced for P-Fc dyads almost null ground state dipole moments and very low values for P-C60 dyads and Fc-P-C60 triads, our EFISH results suggested a significant contribution to γ_EFISH of the purely electronic cubic term γ(−2ω; ω, ω, 0), which prevails on the quadratic dipolar orientational one μβ(−2ω; ω, ω)/5kT, as confirmed by computational evidence.     

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C₂O₄)]·1.5H₂O}_n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu₃(bpy)₃(CH₃OH)(H₂O)(C₂O₄)₄][Cu(bpy)Cr(C₂O₄)₃]·CH₂Cl₂·CH₃OH·H₂O}_n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C₂O₄)]_n of 1, with intra-chain super-exchange interaction 𝐽 = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C₂O₄)₃]_nⁿ⁻ (Cr2–Cu4) with alternating [Cr(C₂O₄)₃]³⁻ and [Cu(bpy)]²⁺ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H₂O)(µ-C₂O₄)Cu(bpy)(CH₃OH)]²⁺ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) comprising three different metal centers (Ca²⁺, Cr³⁺ and Cu²⁺) oxalate-bridged, contains Ca²⁺ atoms as nodes connected with four Cr³⁺ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (6⁶) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [Cu^IICr^III], whose mutual interaction could possibly originate through the spin polarization of Ca²⁺ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.     

Syntheses and a Solid State Structure of a Dinuclear Molybdenum(V) Complex with Pyridine

A mononuclear complex [MoOCl₄(H₂O)]⁻ readily forms a metal−metal bonded {Mo₂O₄}²⁺ core. A high content of pyridine in the reaction mixture prevents further aggregation of dinuclear cores into larger clusters and a neutral, dinuclear complex with the [Mo₂O₄Cl₂(Py)₄] composition is isolated as a product. Solid state structures of two compounds containing this complex, [Mo₂O₄Cl₂(Py)₄]·2.25Py (1) and [Mo₂O₄Cl₂(Py)₄]·1.5PyHCl (2), were investigated by X-ray crystallography.     

The Photoluminescent Properties of New Cationic Iridium(III) Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes

Three cationic iridium(III) complexes [Ir(ppy)₂(phen)][PF₆] (C1), [Ir(ppy)₂(phen)]₂SiF₆ (C2) and [Ir(ppy)₂(phen)]₂TiF₆ (C3) (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline) using different anions were synthesized and characterized by ¹H Nuclear magnetic resonance (¹HNMR), mass spectra (MS), Fourier transform infrared (FTIR) spectra and element analysis (EA). After the ultraviolet visible (UV-vis) absorption spectra, photoluminescent (PL) properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs) as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y₃Al₅O₁₂:Ce³⁺ (YAG). The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W⁻¹ and 11.41 Lm·W⁻¹, respectively.     

Structural,Thermal, and Vibrational Properties of N,N-Dimethylglycine–Chloranilic Acid—A New Co-Crystal Based on an Aliphatic Amino Acid

The new complex of N,N-Dimethylglycine (DMG) with chloranilic acid (CLA) was synthesized and examined for thermal, structural, and dynamical properties. The structure of the reaction product between DMG and CLA was investigated in a deuterated dimethyl sulfoxide (DMSO-d6) solution and in the solid state by Nuclear Magnetic Resonance (NMR) (Cross Polarization Magic Angle Spinning-CPMAS NMR). The formation of the 1:1 complex of CLA and DMG in the DMSO solution was also confirmed by diffusion measurement. X-ray single crystal diffraction results revealed that the N,N-dimethylglycine–chloranilic acid (DMG⁺–CLA⁻) complex crystallizes in the centrosymmetric triclinic P-1 space group. The X-ray diffraction and NMR spectroscopy show the presence of the protonated form of N,N-dimethylglycine and the deprotonated form of chloranilic acid molecules. The vibrational properties of the co-crystal were investigated by the use of neutron (INS), infrared (IR), and Raman (RS) spectroscopies, as well as the density functional theory (DFT) with periodic boundary conditions. From the band shape analysis of the N–CH₃ bending vibration, we can conclude that the CH₃ groups perform fast (τ_R ≈ 10⁻¹¹ to 10^‒13 s) reorientational motions down to a temperature of 140 K, with activation energy at ca. 6.7 kJ mol⁻¹. X-ray diffraction and IR investigations confirm the presence of a strong N⁺–H···O⁻ hydrogen bond in the studied co-crystal.