Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study

Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh₃, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf^??Me₂S<2,6‐lutidine<4‐picoline<CF₃CO₂^?≈DMAP<TMTU<PPh₃<OH^?≈Cl^?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh₃ causes abstraction of one gold atom to give mononuclear complexes LLAuPPh₃⁺ and (Ph₃P)_nAu⁺, but other N and S ligands give ordinary dicationic species LL(AuNu)₂²⁺. In reactions with different bases, LAu⁺ provided new oxonium ions whose chemistry was also studied: (DTBPAu)₃O⁺, (L2Au)₂OH⁺, (L2Au)₃O⁺, (L3Au)₂OH⁺, and (IMesAu)₂OH⁺. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)₂OH⁺, (L2Au)₃O⁺, and L2AuOH are described. Reactions of dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)₂]₃O₂²⁺, L8(Au)₂OH⁺, and [L8(Au)₂]₃O₂²⁺, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe⁺ with S^2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined.     

Solvent Effect and Reactivity Trend in the Aerobic Oxidation of 1,3‐Propanediols over Gold Supported on Titania: NMR Diffusion and Relaxation Studies

In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO₂ catalyst in the aerobic oxidation of 1,4‐butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3‐propanediol and its two methyl‐substituted homologues, 2‐methyl‐1,3‐propanediol and 2,2‐dimethyl‐1,3‐propanediol, over a Au/TiO₂ catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non‐invasive characterisation tools for catalytic materials, which complement conventional reaction data.     

Podophyllotoxin extraction from Linum usitatissimum plant and its anticancer activity against HT‐29, A‐549 and MDA‐MB‐231 cell lines with and without the presence of gold nanoparticles

In recent years, gold nanoparticles (Au‐NPs) have been taken into consideration in nanomedicine due to their excellent biocompatibility, chemical stability and promising optical properties. In this research, podophyllotoxin conjugated with gold nanoparticles (Au‐NPs‐POT) was synthesized and the conjugation of POT with Au‐NPs was confirmed using scanning electron microscopy, mass spectrometry and Fourier transform infrared spectroscopy. The anticancer effects of the product on preclinical models of lung, colon and breast cancers were investigated using MTT test. The analyses showed a direct dose–response relationship. It was found that higher concentrations of POT have more positive effects on the inhibition of cancer cell growth. At POT concentrations of 1, 2.5, 5, 7.5, 10, 15 and 20 ng ml^?1, approximately 50% of the growth of colorectal, lung and breast cancer cell lines was inhibited, while similar results were obtained in the presence of 1, 2, 3, 4 and 5 μg ml^?1 Au‐NPs‐POT. Au‐NPs‐POT exhibited the lowest cytotoxicity due to the presence of POT. The anticancer feature of Au‐NPs‐POT proved the potential to develop better anticancer therapeutics and to open new avenues for treatment of cancers.     

A Novel Solid‐state Electrochemiluminescent Enantioselective Sensor for Ascorbic Acid and Isoascorbic Acid

A novel, stable, solid‐state and stereoselective electrochemiluminescence (ECL) sensor has been designed to enantioselectively discriminate ascorbic acid (AA) and isoascorbic acid (IAA) by immobilizing Ru(bpy)₃²⁺ (Ru), thiolated β‐cyclodextrin (β‐CD‐SH) and gold/platinum hybrid nanoparticles supported on multiwalled carbon nanotube/silica coaxial nanocables (GP‐CSCN) on glassy carbon electrode. All chemical compounds could be immobilized on the surface of electrode stably through nafion film, and high stereoselectivity could be introduced to the sensor via the synergistic effects of the β‐CD‐SH and GP‐CSCN nanomaterials. When the developed sensor interacted with AA and IAA, obvious difference of ECL intensities was observed, and a larger intensity was obtained from AA, which indicated that this strategy could be employed to enantioselectively recognize AA and IAA. As a result, ECL technique might act as a promising method for recognition of chiral compounds.     

Near-Infrared Spectrum of the First Excited State of Au2+

Au₂⁺ is a simple but crucial model system for understanding the diverse catalytic activity of gold. While the Au₂⁺ ground state (X²Σ_g⁺) is understood reasonably well from mass spectrometry and computations, no spectroscopic information is available for its first excited state (A²Σ_u⁺). Herein, we present the vibrationally resolved electronic spectrum of this state for cold Ar-tagged Au₂⁺ cations. This exceptionally low-lying and well isolated A²Σ_(u)⁺←X²Σ_(g)⁺ transition occurs in the near-infrared range. The observed band origin (5738 cm⁻¹, 1742.9 nm, 0.711 eV) and harmonic Au−Au and Au−Ar stretch frequencies (201 and 133 cm⁻¹) agree surprisingly well with those predicted by standard time-dependent density functional theory calculations. The linearly bonded Ar tag has little impact on either the geometric or electronic structure of Au₂⁺, because the Au₂⁺⋅⋅⋅Ar bond (∼0.4 eV) is much weaker than the Au−Au bond (∼2 eV). As a result of 6 s←5d excitation of an electron from the antibonding σ_u^* orbital (HOMO-1) into the bonding σ_g orbital (SOMO), the Au−Au bond contracts substantially (by 0.1 Å).