A common allele of HLA is associated with asymptomatic SARS-CoV-2 infection.

Studies have demonstrated that at least 20% of individuals infected with SARS-CoV-2 remain asymptomatic1-4. Although most global efforts have focused on severe illness in COVID-19, examining asymptomatic infection provides a unique opportunity to consider early immunological features that promote rapid viral clearance. Here, postulating that variation in the human leukocyte antigen (HLA) loci may underly processes mediating asymptomatic infection, we enrolled 29,947 individuals, for whom high-resolution HLA genotyping data were available, in a smartphone-based study designed to track COVID-19 symptoms and outcomes. Our discovery cohort (n = 1,428) comprised unvaccinated individuals who reported a positive test result for SARS-CoV-2. We tested for association of five HLA loci with disease course and identified a strong association between HLA-B*15:01 and asymptomatic infection, observed in two independent cohorts. Suggesting that this genetic association is due to pre-existing T cell immunity, we show that T cells from pre-pandemic samples from individuals carrying HLA-B*15:01 were reactive to the immunodominant SARS-CoV-2 S-derived peptide NQKLIANQF. The majority of the reactive T cells displayed a memory phenotype, were highly polyfunctional and were cross-reactive to a peptide derived from seasonal coronaviruses. The crystal structure of HLA-B*15:01-peptide complexes demonstrates that the peptides NQKLIANQF and NQKLIANAF (from OC43-CoV and HKU1-CoV) share a similar ability to be stabilized and presented by HLA-B*15:01. Finally, we show that the structural similarity of the peptides underpins T cell cross-reactivity of high-affinity public T cell receptors, providing the molecular basis for HLA-B*15:01-mediated pre-existing immunity.

Increased glutaminyl cyclase activity in brains of Alzheimer's disease individuals.

Glutaminyl cyclases (QC) catalyze the formation of neurotoxic pGlu-modified amyloid-ß peptides found in the brains of people with Alzheimer's disease (AD). Reports of several-fold increases in soluble QC (sQC) expression in the brain and peripheral circulation of AD individuals has prompted the development of QC inhibitors as potential AD therapeutics. There is, however, a lack of standardized quantitative data on QC expression in human tissues, precluding inter-laboratory comparison and validation. We tested the hypothesis that QC is elevated in AD tissues by quantifying levels of sQC protein and activity in post-mortem brain tissues from AD and age-matched control individuals. We found a modest but statistically significant increase in sQC protein, which paralleled a similar increase in enzyme activity. In plasma samples sourced from the Australian Imaging, Biomarker and Lifestyle study we determined that QC activity was not different between the AD and control group, though a modest increase was observed in female AD individuals compared to controls. Plasma QC activity was further correlated with levels of circulating monocytes in AD individuals. These data provide quantitative evidence that alterations in QC expression are associated with AD pathology.

Heterobimetallic N-Heterocyclic Carbene Complexes: A Synthetic, Spectroscopic, and Theoretical Study.

A new synthetic methodology has been developed for the preparation of heterobimetallic group 11 and group 12 complexes of a symmetrical bis-NHC "pincer" ligand. The synthetic route involved the initial preparation of a mononuclear [Au(NHC)2](+) complex with pendent imidazole moieties on the NHC ligands. Subsequent alkylation of the imidazole groups with Et3OBF4 and metalation with a second metal ion (Ag(I) or Hg(II)) provided two heterobimetallic complexes. Four homobimetallic (Cu(I)2, Ag(I)2, Au(I)2, and Hg(II)2) complexes of the same bis-NHC "pincer" ligand were also prepared. The homobimetallic Cu(I)2, Au(I)2, and Hg(II)2 complexes and heterobimetallic Au(I)-Ag(I) and Au(I)-Hg(II) complexes and the synthetic intermediates for the heterobimetallic complexes were characterized by X-ray crystallography. These X-ray structures show that the bimetallic complexes adopt "twisted" conformations in the solid state, supporting short M···M interactions. Crystalline samples of the homobimetallic Ag(I)2 and Au(I)2 and heterobimetallic Au(I)-Ag(I) and Au(I)-Hg(II) complexes were emissive at room temperature and at 77 K. The geometries of the synthesized complexes were optimized at the M06-L/def2-SVP level of theory, and the electronic nature of the M···M interactions for all synthesized complexes was investigated using natural bond orbital (NBO) calculations.

Access to the Parent Tetrakis(pyridine)gold(III) Trication, Facile Formation of Rare Au(III) Terminal Hydroxides, and Preliminary Studies of Biological Properties.

In this paper we report on the use of [NO][BF4] to access tricationic tetrakis(pyridine)gold(III) from Au powder, a species inaccessible using the more traditional (tetrahydrothiophene)AuCl route. It is then demonstrated that this family of compounds can be used to access new terminal Au(III) hydroxides, a challenging class of compounds, and the first crystallographically characterized examples employing bidentate ligands. Finally, preliminary biological studies indicate good activity for derivatives featuring polydentate ligands against the HeLa and PC3 cell lines but also strong inhibition of primary HUVEC cells.

The fate of NHC-stabilized dicarbon.

The attempted synthesis of NHC-stabilized dicarbon (NHC=C=C=NHC) through deprotonation of a doubly protonated precursor ([NHC-CH=CH-NHC](2+) ) is reported. Rather than deprotonation, a clean reduction to NHC=CH-CH=NHC is observed with a variety of bases. The apparent resistance towards deprotonation to the target compound led to a reinvestigation of the electronic structure of NHC→CC←NHC, which showed that the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) gap is likely too small to allow for isolation of this species. This is in contrast to the recent isolation of the cyclic alkylaminocarbene analogue (cAAC=C=C=cAAC), which has a large HOMO-LUMO gap. A detailed theoretical study illuminates the differences in electronic structures between these molecules, highlighting another case of the potential advantages of using cAAC rather than NHC as a ligand. The bonding analysis suggests that the dicarbon compounds are well represented in terms of donor-acceptor interactions L→C2 ←L (L=NHC, cAAC).

Facile formation of homoleptic Au(III) trications via simultaneous oxidation and ligand delivery from [PhI(pyridine)2](2+).

We report the first examples of Au(III) tricationic complexes bound only by neutral monodentate ligands, which are a new class of gold reagents. Oxidative addition to the bis-pyridine Au(I) cation, [Au(4-DMAP)2](+), using a series of dicationic I(III) oxidants of the general form [PhI(L)2](2+) (L = pyridine, 4-DMAP, 4-cyanopyridine) allows ready access to homoleptic and pseudo-homoleptic Au(III) complexes [Au(4-DMAP)2(L)2](3+). The facile oxidative addition of Au(I) species additionally demonstrates the efficacy of PhI(L)2](2+) reagents as halide-free oxidants for Au(I). Comparisons are made via attempts to oxidize NHC-Au(I)Cl, where introduction of the chloride anion results in complex mixtures via ligand and chloride exchange, demonstrating the advantage of using the pyridine-based homoleptic compounds. The new Au(III) trications show intriguing reactivity with water, yielding dinuclear oxo-bridged and rare terminal Au(III)-OH complexes.

Understanding electrogenerated chemiluminescence efficiency in blue-shifted iridium(III)-complexes: an experimental and theoretical study.

Compared to tris(2-phenylpyridine)iridium(III) ([Ir(ppy)3 ]), iridium(III) complexes containing difluorophenylpyridine (df-ppy) and/or an ancillary triazolylpyridine ligand [3-phenyl-1,2,4-triazol-5-ylpyridinato (ptp) or 1-benzyl-1,2,3-triazol-4-ylpyridine (ptb)] exhibit considerable hypsochromic shifts (ca. 25-60 nm), due to the significant stabilising effect of these ligands on the HOMO energy, whilst having relatively little effect on the LUMO. Despite their lower photoluminescence quantum yields compared with [Ir(ppy)3 ] and [Ir(df-ppy)3 ], the iridium(III) complexes containing triazolylpyridine ligands gave greater electrogenerated chemiluminescence (ECL) intensities (using tri-n-propylamine (TPA) as a co-reactant), which can in part be ascribed to the more energetically favourable reactions of the oxidised complex (M(+) ) with both TPA and its neutral radical oxidation product. The calculated iridium(III) complex LUMO energies were shown to be a good predictor of the corresponding M(+) LUMO energies, and both HOMO and LUMO levels are related to ECL efficiency. The theoretical and experimental data together show that the best strategy for the design of efficient new blue-shifted electrochemiluminophores is to aim to stabilise the HOMO, while only moderately stabilising the LUMO, thereby increasing the energy gap but ensuring favourable thermodynamics and kinetics for the ECL reaction. Of the iridium(III) complexes examined, [Ir(df-ppy)2 (ptb)](+) was most attractive as a blue-emitter for ECL detection, featuring a large hypsochromic shift (λmax =454 and 484 nm), superior co-reactant ECL intensity than the archetypal homoleptic green and blue emitters: [Ir(ppy)3 ] and [Ir(df-ppy)3 ] (by over 16-fold and threefold, respectively), and greater solubility in polar solvents.

Rhenium and technetium tricarbonyl complexes of N-heterocyclic carbene ligands.

A strategy for the conjugation of N-heterocyclic carbene (NHC) ligands to biomolecules via amide bond formation is described. Both 1-(2-pyridyl)imidazolium or 1-(2-pyridyl)benzimidazolium salts functionalized with a pendant carboxylic acid group were prepared and coupled to glycine benzyl ester using 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide. A series of 10 rhenium(I) tricarbonyl complexes of the form [ReX(CO)3(CN)] (CN is a bidentate NHC ligand, and X is a monodentate anionic ligand: Cl(-), RCO2(-)) were synthesized via a Ag2O transmetalation protocol from the Re(I) precursor compound Re(CO)5Cl. The synthesized azolium salts and Re(I) complexes were characterized by elemental analysis and by (1)H and (13)C NMR spectroscopy, and the molecular structures for one imidazolium salt and seven Re(I) complexes were determined by single-crystal X-ray diffraction. (1)H NMR and mass spectrometry studies for an acetonitrile-d3 solution of [ReCl(CO)3(1-(2-pyridyl)-3-methylimidazolylidene)] show that the monodentate chloride ligand is labile and exchanges with this solvent yielding a cationic acetonitrile adduct. For the first time the labeling of an NHC ligand with technetium-99m is reported. Rapid Tc-99m labeling was achieved by heating the imidazolium salt 1-(2-pyridyl)-3-methylimidazolium iodide and Ag2O in methanol, followed by the addition of fac-[(99m)Tc(OH2)3(CO)3](+). To confirm the structure of the (99m)Tc-labeled complex, the equivalent (99)Tc complex was prepared, and mass spectrometric studies showed that the formed Tc complexes are of the form [(99m/99)Tc(CH3CN)(CO)3(1-(2-pyridyl)-3-methylimidazolylidene)](+) with an acetonitrile molecule coordinated to the metal center.

Triamidetriamine bearing macrobicyclic and macrotricyclic ligands: potential applications in the development of copper-64 radiopharmaceuticals.

A versatile and straightforward synthetic approach is described for the preparation of triamide bearing analogues of sarcophagine hexaazamacrobicyclic cage ligands without the need for a templating metal ion. Reaction of 1,1,1-tris(aminoethyl)ethane (tame) with 3 equiv of 2-chloroacetyl chloride, yields the tris(α-chloroamide) synthetic intermediate 6, which when treated with either 1,1,1-tris(aminoethyl)ethane or 1,4,7-triazacyclononane furnished two novel triamidetriamine cryptand ligands (7 and 8 respectively). The Co(III) and Cu(II) complexes of cryptand 7 were prepared; however, cryptand 8 could not be metalated. The cryptands and the Co(III) complex 9 have been characterized by elemental analysis, (1)H and (13)C NMR spectroscopy, and X-ray crystallography. These studies confirm that the Co(III) complex 9 adopts an octahedral geometry with three facial deprotonated amido-donors and three facial amine donor groups. The Cu(II) complex 10 was characterized by elemental analysis, single crystal X-ray crystallography, cyclic voltammetry, and UV-visible absorption spectroscopy. In contrast to the Co(III) complex (9), the Cu(II) center adopts a square planar coordination geometry, with two amine and two deprotonated amido donor groups. Compound 10 exhibited a quasi-reversible, one-electron oxidation, which is assigned to the Cu(2+/3+) redox couple. These cryptands represent interesting ligands for radiopharmaceutical applications, and 7 has been labeled with (64)Cu to give (64)Cu-10. This complex showed good stability when subjected to L-cysteine challenge whereas low levels of decomplexation were evident in the presence of L-histidine.

Experimental and theoretical studies of pH-responsive iridium(III) complexes of azole and N-heterocyclic carbene ligands.

A series of nine luminescent iridium(III) complexes with pH-responsive imidazole and benzimidazole ligands have been prepared and characterized. The first series of complexes were of the form [Ir(ppy)2(N^N)]+ or [Ir(ppy)2(C^N)]+ (where ppy is 2-phenylpyridine and N^N is 2-(2-pyridyl)imidazole or 2-(2-pyridyl)benzimidazole and C^N represents a pyridyl-triazolylidene-based N-heterocyclic carbene ligand). For these complexes, the benzimidazole group was either unsubstituted or substituted with electron-withdrawing (Cl) or electron-donating (Me) groups. The second series of complexes were of the form [Ir(phbim)2(N^N)]+ or [Ir(phbim)2(C^N)]+ (where phbim is 2-phenylbenzimidazole and N^N is either 2,2'-bipyridine or 1,10-phenanthroline and C^N is either a pyridyl-imidazolylidene or pyridyl-triazolylidene N-heterocyclic carbene ligand). UV-visible and photoluminescence pH titration studies showed that changing the protonation state of these complexes results in significant changes in the photoluminescence emission properties. The pKa values of prepared complexes were estimated from the spectroscopic pH titration data and these values show that the nature of the pH-sensitive ligands (either main or ancillary ligands) resulted in a significant capacity to modulate the pKa values for these compounds with values ranging from 5.19-11.22. Theoretical investigations into the nature of the electronic transitions for the different protonation states of compounds were performed and the results were consistent with the experimental results.

Electrochemiluminescent ruthenium(II) N-heterocyclic carbene complexes: a combined experimental and theoretical study.

A series of four Ru(II) complexes of the form [Ru(bpy)2(C(^)N)](2+) (where C(^)N is a bidentate pyridine-functionalized imidazolylidene- or benzimidazolylidene-based N-heterocyclic carbene (NHC) ligand and bpy is 2,2'-bipyridine) have been synthesized using a Ag(I) transmetalation protocol from the Ru(II) precursor compound, Ru(bpy)2Cl2. The synthesized azolium salts and Ru(II) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy, cyclic voltammetry, and electronic absorption and emission spectroscopy. The molecular structures for two benzimidazolium salts and three Ru(II) complexes were determined by single crystal X-ray diffraction. The complexes display photoluminescence within the range 611-629 nm, with the emission wavelength of the benzimidazolylidene containing structures, slightly blue-shifted relative to the imidazolylidene containing complexes. All complexes exhibited a reversible, one-electron oxidation, which is assigned to the Ru(2+/3+) redox couple. When compared to [Ru(bpy)3](2+), complexes of imidazolylidene containing ligands were oxidized at more negative potentials, while those of the benzimidazolylidene containing ligands were oxidized at more positive potentials. All four complexes exhibited moderately intense electrochemiluminescence (ECL) with the obtained ECL spectra closely resembling the photoluminescence spectra. The ability to predictably fine-tune the highest occupied molecular orbital (HOMO) level of the Ru(II) complexes via the flexible synthetic strategy offered by NHCs is valuable for the design of ECL-based multiplexed detection strategies.

Diverse reactions of PhI(OTf)2 with common 2-electron ligands: complex formation, oxidation, and oxidative coupling.

The crystal structures of bis-pyridine stabilized iodine dications [PhI(pyr)(2)](2+) are reported as triflate salts, representing the first ligand supported iodine dications to be structurally characterized. The pyridine complexes are susceptible to ligand exchange in reaction with stronger N-based donors such as 4-dimethylaminopyridine. Attempts to extend this reactivity to N-heterocyclic carbene and phosphine ligands, as has been accomplished in the earlier p-block groups, resulted in redox chemistry, with oxidation of the ligands rather than coordination.

Cytotoxic properties of rhenium(I) tricarbonyl complexes of N-heterocyclic carbene ligands.

A family of eight rhenium(I) tricarbonyl complexes bearing pyridyl-imidazolylidene or bis-imidazolylidene ligands in combination with a series of N-acetyl amino acids ligands (glycine, isoleucine, and proline) and an acetate have been synthesised and characterised. These complexes are of interest as potential anticancer agents, where the oxygen bound carboxylate ligand can exchange with water giving rise to cytotoxic cationic complexes. The pseudo-first-order aquation rate constants for the complexes were evaluated using 1H NMR time-course experiments and for the complexes of the bis-imidazolylidene ligand the average k1 value was 6.22 × 10-5 s-1 while for the pyridyl-imidazolylidene ligand the aquation rate was slower with the average k1 value being 3.00 × 10-5 s-1. Cytotoxicity studies in three cancer cell lines (MDA-MB-231, PC3 and HEPG2) showed that the Re(I) complexes of the bis-imidazolylidene ligand were significantly more toxic than those of the pyridyl-imidazolylidene ligand.

Antibacterial silver and gold complexes of imidazole and 1,2,4-triazole derived N-heterocyclic carbenes.

A series of gold(I) (4a-4h, 5a-5b) and silver(I) (3a-3h) complexes of 1,2,4-triazolylidene and imidazolylidene based N-heterocyclic carbene ligands were prepared and the antibacterial activities of these complexes have been evaluated. The complexes were characterised using 1H-NMR, 13C-NMR, HRMS and in the cases of 3a, 3c, 4b and 5b by X-ray crystallography. The gold(I) complexes with phenyl substituents (4a-4d) were found to have potent antibacterial activity against Gram-positive bacteria, with the complexes of the 1,2,4-triazolylidene ligands being more active (4c, MIC = 4-8 µg mL-1 against Enterococcus faecium and 2 µg mL-1 against Staphylococcus aureus) than the analogous imidazolylidene complexes 4a and 4b (4a, MIC = 64 µg mL-1 against E. faecium and 2-4 µg mL-1 against S. aureus). Two of the silver(I) complexes have promising antibacterial activity against Acinetobacter baumannii (3f, MIC = 2-4 µg mL-1 and 3g, MIC = 2 µg mL-1). Silver(I) complex 3f and gold(I) complex 4c were tested against multi-drug resistant bacterial strains and high levels of antibacterial activity were observed. The potential for antibacterial resistance to develop against these metal containing complexes was investigated and significantly, no resistance was observed upon continuous treatment, whilst resistance was developed against the widely used broad-spectrum antibiotic ciprofloxacin in the same bacterial strains, under the conditions tested. The solution and gas phase stabilities of the complexes have been investigated using a combination of 1H-NMR, HRMS and detailed computational mechanistic studies were undertaken to gain insights into the possible decomposition reactions for silver complexes in aqueous solution.

Ablation of CD8+ T cell recognition of an immunodominant epitope in SARS-CoV-2 Omicron variants BA.1, BA.2 and BA.3.

The emergence of the SARS-CoV-2 Omicron variant has raised concerns of escape from vaccine-induced immunity. A number of studies have demonstrated a reduction in antibody-mediated neutralization of the Omicron variant in vaccinated individuals. Preliminary observations have suggested that T cells are less likely to be affected by changes in Omicron. However, the complexity of human leukocyte antigen genetics and its impact upon immunodominant T cell epitope selection suggests that the maintenance of T cell immunity may not be universal. In this study, we describe the impact that changes in Omicron BA.1, BA.2 and BA.3 have on recognition by spike-specific T cells. These T cells constitute the immunodominant CD8+ T cell response in HLA-A*29:02+ COVID-19 convalescent and vaccinated individuals; however, they fail to recognize the Omicron-encoded sequence. These observations demonstrate that in addition to evasion of antibody-mediated immunity, changes in Omicron variants can also lead to evasion of recognition by immunodominant T cell responses.

A luminescent lipid mimetic iridium(III) N-heterocyclic carbene complex for membrane labelling.

Labelling phospholipid membranes with luminophores without altering the biophysical characteristics of the system is particularly challenging due to the small size of the phospholipid molecules and the sensitivity of membrane properties to the presence of fused heterocyclic molecules. Here the design and synthesis of a luminescent lipid mimetic Ir(III) N-heterocyclic carbene complex of the form [Ir(ppy)2(C^N)] (where ppy = 2-(phenyl)-pyridine and C^N is a N-heterocyclic carbene ligand) conjugated to stearic acid is described. This complex was synthesised by the reaction of an acetate functionalised Ir(III) precursor complex with tert-butyl N-(2-aminoethyl)carbamate (mono-BOC protected ethylene diamine) and after deprotection of the amine group this complex was coupled to stearic acid using the peptide coupling reagent 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC). The photophysical properties of the synthesised complexes were evaluated and they showed blue-green luminescence in the range of 514-520 nm. Fluorescence microscopy studies showed that the lipid mimetic complex successfully incorporated into liposomes composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), while dynamic light scattering (DLS) and differential scanning calorimetry (DSC) studies showed that the complex had negligible influence on the biophysical properties of the liposomes.

Charge neutral rhenium tricarbonyl complexes of tridentate N-heterocyclic carbene ligands that bind to amyloid plaques of Alzheimer's disease.

Two tridentate ligand systems bearing N-heterocyclic carbene (NHC), amine and carboxylate donor groups coupled to benzothiazole- or stilbene-based amyloid binding moieties were synthesised. Reaction of the imidazolium salt containing pro-ligands with Re(CO)5Cl yielded the corresponding rhenium metal complexes which were characterised by NMR, and X-ray crystallography. These ligands are of interest for the potential preparation of technetium-99m imaging agents for Alzheimer's disease and the capacity of these rhenium complexes bind to amyloid fibrils composed of amyloid-ß peptide and amyloid plaques in human frontal cortex brain tissue was evaluated using fluorescence microscopy. These studies show that the complexes bound efficiently to amyloid-ß fibrils and some evidence of binding to amyloid-ß plaques.

Luminescent iridium(iii)-boronic acid complexes for carbohydrate sensing.

A family of four Ir(iii) complexes of the form [Ir(ppy)2(L)]Cl (where ppy = 2-phenyl-pyridine and L = a pyridyl-1,2,4-triazole or pyridyl-1,3,4-oxadiazole ligand bearing a boronic acid group) have been prepared as potential luminescent sensors for carbohydrates. A modular eight step procedure was developed to synthesise the complexes, and this was initiated with the preparation of two benzhydrazide and three S-ethylated pyridine-2-thiocarboxamides precursors. Reaction of these precursors produced three new 1,2,4-triazole- and one 1,3,4-oxadiazole-based ligands substituted with boronic acid pinacol ester groups. The boronic acid pinacol esters were then converted to boronic acids in two steps via potassium trifluoroborate intermediates. The boronic acid substituted ligands and their Ir(iii) complexes were fully characterised using a range of techniques including X-ray crystallography in the case of the pyridyl-1,3,4-oxadiazole ligand and two of the Ir(iii) complexes. The capacity of the synthesised Ir(iii) complexes to form boronic acid cyclic esters with the simple sugars glucose and fructose was evaluated using high-resolution mass spectrometry (HRMS) and photoluminescence titration studies. These studies confirm that the Ir(iii) complexes form adducts with both glucose and fructose, with increased levels of boronic acid cyclic esters being formed with fructose at higher pHs. Theoretical calculations were used to gain insight into the nature of the electronic transitions involved in the electronic absorption and emission spectra.

Synthesis, conformational analysis and antibacterial activity of Au(I)-Ag(I) and Au(I)-Hg(II) heterobimetallic N-heterocyclic carbene complexes.

A post-synthetic modification and metallation procedure has been used to prepare a family of heterobimetallic Au(i)-Ag(i) and Au(i)-Hg(ii) complexes featuring either symmetrical or asymmetrical bis-N-heterocyclic carbene ligands with methylene or ethylene linker groups. This synthetic approach is versatile and allows for the synthesis of heterobimetallic complexes bearing asymmetrical ligands that differ in the nature of the NHC wingtip substituents (dimethyl, diethyl or ethyl-methyl) and for the selective placement of the different metal ions. The synthesised complexes were characterised using 1H and 13C NMR spectroscopy and high resolution mass spectrometry (HR-MS) and in the case of complexes 4a, 5b and 8b by X-ray crystallography. The complexes of the methylene linked bridging ligands display conformational isomerism in solution and the conformations adopted by selected compounds were examined using variable temperature (VT) 1H NMR studies. The antibacterial properties of the heterobimetallic Au(i)-Ag(i) complexes in addition to the corresponding homobimetallic Ag(i)2, Au(i)2 complexes were evaluated against clinically relevant Gram-positive and Gram-negative bacterial strains. The homobimetallic Au(i)2 complex and precursor pro-ligand displayed no antibacterial activity up to 256 µg mL-1, whereas the homobimetallic Ag(i)2 was active against all Gram-positive and Gram-negative bacterial strains tested (MIC = 8-32 µg mL-1). Interestingly, both Au(i)-Ag(i) heterobimetallic complexes displayed similar broad-spectrum activity (MIC = 4-32 µg mL-1) to the Ag(i)2 homobimetallic complex.

Near-Infrared Electrochemiluminescence from Bistridentate Ruthenium(II) Di(quinoline-8-yl)pyridine Complexes in Aqueous Media.

We report the synthesis, photophysics, electrochemistry and electrochemiluminescence (ECL) of two dqp (dqp=2,6-di(quinoline-8-yl)pyridine) based ruthenium(II) complexes, bearing either a n-butyl ester (1) or the corresponding carboxylic acid functionality (2). The complexes were prepared from [Ru(dqp)(MeCN)3 ][PF6 ]2 by reaction with the dqp precursor using microwave irradiation. In both cases, photoluminescence spectra present strong 3 MLCT-based red/near-infrared (NIR) emissions centred at about 710 nm. The photoluminescence quantum yields were 6.1 % and 1.8 % for 1 and 2 respectively while the excited state lifetimes were 3.60 µs and 2.37 µs. Both complexes are ECL active, although ECL efficiency (ΦECL ) of 1 was substantially higher than 2, due to its more favourable electrochemical properties. Importantly, 1 also gave strong ECL in aqueous media, which is rare for near-infrared emitters. The results suggest the possibility of very interesting ECL sensing applications for this class of emitter in biological media.