The first solid-state route to luminescent Au(I)-glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au(SG) nanoclusters for application in cancer radiotheraphy.

There is still a need for synthetic approaches that are much faster, easier to scale up, more robust and efficient for generating gold(I)-thiolates that can be easily converted into gold-thiolate nanoclusters. Mechanochemical methods can offer significantly reduced reaction times, increased yields and straightforward recovery of the product, compared to the solution-based reactions. For the first time, a new simple, rapid and efficient mechanochemical redox method in a ball-mill was developed to produce the highly luminescent, pH-responsive Au(I)-glutathionate, [Au(SG)].

Broadband measurement of true transverse relaxation rates in systems with coupled protons: application to the study of conformational exchange.

Accurate measurement of transverse relaxation rates in coupled spin systems is important in the study of molecular dynamics, but is severely complicated by the signal modulations caused by scalar couplings in spin echo experiments. The most widely used experiments for measuring transverse relaxation in coupled systems, CPMG and PROJECT, can suppress such modulations, but they also both suppress some relaxation contributions, and average relaxation rates between coupled spins. Here we introduce a new experiment which for the first time allows accurate broadband measurement of transverse relaxation rates of coupled protons, and hence the determination of exchange rate constants in slow exchange from relaxation measurements.

Mechanochemical synthesis of mononuclear gold(I) halide complexes of diphosphine ligands with tuneable luminescent properties.

A mechanochemical method is reported for the synthesis of Au(diphos)X complexes of diphosphine (diphos = XantPhos and -XantPhos) ligands and halide ions (X = Cl and I). The Au(XantPhos)X (1: X = Cl; 2: X = I) and Au(-XantPhos)Cl (3) complexes exhibited either yellowish green (1) or bluish green (2) emission, whereas 3 was seemingly non-emissive in the solid state at room temperature. Blue- (2B) and bluish green (2G) luminescent concomitant solvates of 2 were obtained by recrystallization.

An unusual case of childhood osteoarticular tuberculosis from the Árpádian Age cemetery of Győrszentiván-Révhegyi tag (Győr-Moson-Sopron county, Hungary).

Ancient human remains exhibiting bony changes consistent with osteoarticular tuberculosis (OATB) indicate that the disease has afflicted mankind for millennia. Nonetheless, not many pediatric OATB cases have been published in the paleopathological literature-from Hungary, only three cases have been described up to now. In our paper, we demonstrate a child (S0603) from the Árpádian Age cemetery of Győrszentiván-Révhegyi tag (northwestern Hungary), who represents a unique case of OATB regarding both the pattern and severity of the observed bony changes.

Unexpected formation of a fused double cycle trinuclear gold(i) complex supported by ortho-phenyl metallated aryl-diphosphine ligands and strong aurophilic interactions.

The first homoleptic trinuclear arylgold(i) complex, [Au3(L')2](NO3) (3), based on an ortho-phenyl metallated aryl-diphosphine ligand (L' = o-C6H4PPh(C15H10O)PPh2), has been obtained through a new thermolytic reaction of the corresponding diauracycle, [Au2(L)2](NO3)2 (L = xantphos). The formation of 3 involves activation of the ortho-phenyl C-H bond of the xantphos ligands. The presence of Au-C bonds in this new gold-diphosphine cluster is not its only remarkable feature, since it also displays two 12-membered rings fused together and a linear {Au3} chain with aurophilic interactions.

Mechano-induced reversible colour and luminescence switching of a gold(i)-diphosphine complex.

A gold(i)-diphosphine simultaneously exhibits reversible mechanochromism and mechanochromic luminescence. The mechanical grinding can trigger a transformation from a neutral mononuclear structure exhibiting white colour and blue photoluminescence to an ionic dinuclear structure with intramolecular aurophilic interactions exhibiting yellow colour and red emission.

Anion-, Solvent-, Temperature-, and Mechano-Responsive Photoluminescence in Gold(I) Diphosphine-Based Dimers.

A series of [Au2 (nixantphos)2](X)2 (nixantphos=4,6-bis(diphenylphosphino)-phenoxazine; X=NO3, 1; CF3 COO, 2; CF3 SO3, 3; [Au(CN)2], 4; and BF4, 5) complexes that exhibit intriguing anion-switchable and stimuli-responsive luminescent photophysical properties have been synthesized and characterized. Depending on their anions, these complexes display yellow (3), orange (4 and 5), and red (1 and 2) emission colors. They exhibit reversible thermo-, mechano-, and vapochromic luminescence changes readily perceivable by the naked eye.

Mechanochemical synthesis of crystalline and amorphous digold(I) helicates exhibiting anion- and phase-switchable luminescence properties.

For the first time, mechanochemical synthesis has been used for the preparation of crystalline and amorphous dinuclear gold(i) helicates, [Au2L2](X)2 (L = xantphos; X = CF3SO3, SCN, BF4 and PF6), that show anion- and phase-switchable luminescence properties. This solid-state approach provides strategies for developing switchable luminescent materials.

A versatile solvent-free mechanochemical route to the synthesis of heterometallic dicyanoaurate-based coordination polymers.

The solid-state mechanochemical method was proved to be a fast, simple, and efficient route to the synthesis of heterometallic [Au(CN)(2)]-based coordination polymers. Thus, a series of mixed-metal complexes, such as KCo[Au(CN)(2)](3), KNi[Au(CN)(2)](3), Cu(H(2)O)(2)[Au(CN)(2)](2), and Zn[Au(CN)(2)](2), was obtained by grinding stoichiometric amounts of K[Au(CN)(2)] and transition metal(II) chlorides. This solid-state method rapidly yields pure dicyanoaurate-based compounds, also in cases when the aqueous solution synthesis leads to an unseparable mixture of products.

Guest escape and uptake in nonporous crystals of a gold(I) macrocycle.

The nonporous gold(I) diphosphine complex [Au(2)(cis-dppe)(2)](NO(3))(2) [1, cis-dppe = cis-1,2-bis(diphenylphosphino)ethylene] is robust enough to trap guests, but at the same time, it is flexible enough to allow guest release without destruction of its crystal lattice. This nonporous gold(I) compound 1 is also efficient at capturing and releasing carbon dioxide in a controlled manner.

[mu-4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene]bis[(trifluoroacetato)gold(I)] and its dichloromethane 0.58-solvate.

The dinuclear Au(I) complex containing the 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) ligand and trifluoroacetate anions exists in a solvent-free form, [mu-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene]bis[(trifluoroacetato)gold(I)], [Au(2)(C(2)F(3)O(2))(2)(C(39)H(32)OP(2))], (I), and as a dichloromethane solvate, [Au(2)(C(2)F(3)O(2))(2)(C(39)H(32)OP(2))].0.58CH(2)Cl(2), (II).

Synthesis and structure of a cyanoaurate-based organotin polymer exhibiting unusual ion-exchange properties.

We synthesized and structurally characterized the first cyanoaurate-based organotin polymer Me(3)Sn[Au(CN)(2)] (1), which exhibits unusual ion-exchange properties. In the structure of 1, the void space of the 2D grids formed via Au..

Solvent-assisted spontaneous resolution of a 16-membered ring containing gold(I) showing short Au...Au aurophilic interaction and a figure-eight conformation.

The achiral 4,6-bis(diphenylphosphino) phenoxazine (nixantphos) ligand was used to synthesize a gold(I) complex, [Au2(nixantphos)2](NO3)2, containing a 16-membered [Au2(nixantphos)2](+2) cationic ring in a chiral figure-eight conformation. The single crystal X-ray diffraction analysis of [Au2(nixantphos)2](NO3)2.3MeOH.

Conformational analysis of a helically distorted gold(I) macrocycle derived from xantphos: evidence for the aurophilic Au--Au interaction from NMR.

Variable-temperature solution (1)H- and (31)P-NMR experiments are reported for [Au(2)(xantphos)(2)](NO(3))(2) gold(I) complex incorporating a 16-membered Au(2)P(4)C(8)O(2) macrocycle derived from the 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos) ligand. These NMR studies provide detailed structural information about its solution structure in comparison to the solid-state structure available from single crystal X-ray diffraction. Two-dimensional (1)H-NOESY spectroscopy at low temperatures allowed the full assignment of proton resonances, which are severely exchange-broadened at room temperature.

Multifocal ERG reveals several patterns of cone degeneration in retinitis pigmentosa with concentric narrowing of the visual field.

Purpose: To analyze multifocal ERGs (mfERGs) in patients with retinitis pigmentosa (RP), with constricted visual fields and visual acuity satisfactory for steady fixation.

Methods: The mfERGs of 86 eyes of 43 patients with various forms of inheritance and durations of RP were analyzed. A retinal scanning system with a 20-in.

Preparation and structural characterization of trimethyltin(IV) tropolonate. Investigation of a rare methyl-migrational dismutation in the solution, solid and liquid states.

The synthesis and structural characterisation, by low temperature X-ray diffraction and solid-state NMR, of the highly reactive monomeric Me(3)Sn(trop) (1) complex has been studied; 1 rearranges into Me(2)Sn(trop)(2) (2) and Me(4)Sn by methyl-transfer dismutation. Based on the NMR kinetic data it appears that complex demethylates faster in the solid and liquid than in dilute CDCl(3) solution, but with a slower rate than in dilute CD(3)OD solution.

Synthesis and solution- and solid-state characterization of gold(I) rings with short Au...Au interactions. Spontaneous resolution of a gold(I) complex.

We report the synthesis and solution- and solid-state characterization of gold(I) rings with short 1,9-transannular Au...

Demethylation of the [Me3Sn(PhN2O2)]4 tetramer into dimeric [Me2Sn(PhN2O2)2]2: a thermally induced methyl-transfer between supramolecules.

The single crystals of tetrameric [Me3Sn(PhN2O2)]4 (1) supramolecule demethylates into single crystals of [Me2Sn(PhN2O2)2]2 dimer (2) and volatile Me4Sn, as a result of a crystal-to-crystal supramolecular structural transformation, which occurs upon heating and it is accompanied by a significant change of the molecular and crystal structures.