Hot-stage microscopy - Direct Analysis in Real-time mass spectrometry (HDM) as a novel tool for monitoring thermally-driven reactions on a small scale.

There is a requirement for reliable real-time analytical tools for reaction monitoring to optimise chemical syntheses. We have developed a new technique which combines thermal analysis, digital microscopy and chemical identification using ambient ionisation mass spectrometry. We term this hot-stage microscopy-Direct Analysis in Real-Time mass spectrometry (HDM).

Application of hot-stage microscopy direct analysis in real time mass spectrometry (HDM) to the analysis of polymers.

Rationale: Polymers are ubiquitous, and characterisation of their chemical, thermal and mechanical properties is important in many applications. Hot-stage microscopy Direct Analysis in Real Time mass spectrometry (HDM) is a new technique which combines optical measurements with the benefits of ambient ionisation mass spectrometry. Physical and chemical information can be obtained as a function of sample temperature, in real time.

Concomitant lipomatous hypertrophy and left atrial mass: Distinguishing benign from malignant.

Masses in and near the interatrial septum may be either benign or malignant. The most common mass near the interatrial septum is lipomatous atrial septal hypertrophy (LASH). LASH can be present in patients with intracardiac malignancies, myxomas, lipomas, or other cardiac masses.

An Integrated Hot-Stage Microscope-Direct Analysis in Real Time-Mass Spectrometry System for Studying the Thermal Behavior of Materials.

This paper describes a new analytical instrument that combines a precisely temperature-controlled hot-stage with digital microscopy and Direct Analysis in Real Time-mass spectrometry (DART-MS) detection. The novelty of the instrument lies in its ability to monitor processes as a function of temperature through the simultaneous recording of images, quantitative color changes, and mass spectra. The capability of the instrument was demonstrated through successful application to four very varied systems including profiling an organic reaction, decomposition of silicone polymers, and the desorption of rhodamine B from an alumina surface.

Formation of a dimer of trinuclear helicates which encapsulates an array of six hydrogen-bonded anions.

The amine-containing ligand L, composed of two bidentate pyridyl-thiazole moieties linked by a 1,3-diaminophenylene unit, reacts with copper(II) ions to form a dinuclear double helicate [Cu2 L2 ](4+) . Reaction of [Cu2 L2 ](4+) with dihydrogen phosphate (0.5 equivalents) gives the unsaturated dinuclear double helicate [Cu2 L2 (OPO3 H2 )](3+) .

Parameters affecting ion intensities in transmission-mode direct analysis in real-time mass spectrometry.

A survey of the effect of temperature, transmission module material and analysis time on ion intensities in transmission mode direct analysis in real time mass spectrometry is presented. Ion intensity profiles obtained for two related compounds are similar when analysed separately but are very different when analysed as a mixture.

Self-assembly of a heteroleptic one-dimensional chain comprising different dinuclear meso-helicates in the solid-state.

We describe two mesocate assemblies that contain either an ethylene glycol or ammonium group which form a heteroleptic one-dimensional infinite chain in the solid state.

Tri-carbonyl-chlorido-(6',7'-di-hydro-5'H-spiro-[cyclo-hexane-1,6'-dipyrido[3,2-d:2',3'-f][1,3]diazepine]-κ(2) N (1),N (11))rhenium(I).

In the title compound, [ReCl(C16H18N4)(CO)3], the Re(I) ion is coordinated in a distorted octa-hedral geometry by one Cl atom, two N atoms of the bidentate ligand and three carbonyl groups. The cyclo-hexane group is orientated in a transoid fashion with respect to the chloride ligand. In the crystal, N-H⋯Cl hydrogen bonds link complex mol-ecules, forming a two-dimensional network parallel to (100).

Tri-carbonyl-chlorido-(6',7'-di-hydro-5'H-spiro-[cyclo-pentane-1,6'-dipyrido[3,2-d:2',3'-f][1,3]diazepine]-κ(2) N (1),N (11))rhenium(I).

In the title compound, [ReCl(C15H16N4)(CO)3], the Re(I) ion is coordinated in a distorted octa-hedral geometry by one Cl atom, two N atoms of the bidentate ligand and three carbonyl groups. The cyclo-pentane group is orientated in a transoid fashion with respect to the chloride ligand. The dihedral angle between the pryridine rings is 10.

Steric control of the formation of dinuclear double helicate and dinuclear meso-helicate assemblies.

We describe a ligand system that forms either a dinuclear double helicate or a dinuclear double mesocate dependent upon the size of the metal ion or the steric bulk of the ligand strand.

Synthesis of ligands containing N-oxide donor atoms and their assembly into metallosupramolecular structures.

A series of ligands that contain both N-donor and N-oxide donor atoms have been synthesised and ligands L5, L6, L7 and L8 contain, 4, 6, 5, and 6 donor atoms respectively. The smallest ligand L5 forms a mononuclear complex with Cu2+ ([Cu(L5)(ClO4)2(MeCN)]) whereas L6 and L7 form dinuclear double helicates with Ni2+ and Cu2+ respectively ([Ni2(L6)2]4+ and [Cu2(L7)2]4+). L8 forms a tetranuclear cyclic helicate upon reaction with Co2+ ([Co4(L8)4]8+) and in all cases the complexes are characterised by single-crystal X-ray diffraction and ESI-MS.

Luminescent rhenium fac-tricarbonyl-containing complexes of androgenic oxo-steroids.

A new route to luminescent derivatives of androgenic steroids containing a ketone group in the 3- or 17-position has been developed. Reaction with the fac-Re(CO)(3)Cl complex of 3,3'-diamino-2,2'-bipyridine (complex 1) afforded a cyclic aminal product with different steroids. The rate of reaction and yield varies according to the conjugation or steric hindrance around the ketone group.

Coordination polymers utilizing N-oxide functionalized host ligands.

Pyridyl functionalized host molecules are oxidized to their N-oxide analogues and form a series of coordination polymers and discrete complexes with transition metal cations. Complex {[Ag(3)(NMP)(6)(L1)(2)]·3(ClO(4))}(∞) where L1 = tris(isonicotinoyl-N-oxide)cyclotriguaiacylene, NMP = N-methylpyrrolidone, is a three-dimensional (3-D) 3,6-connected coordination polymer of pyrite-like (pyr) topology and features ligand unsupported argentophilic interactions, while two-dimensional (2-D) 3,6-connected coordination polymers with the rarely reported kagome dual (kgd) topology are found for [M(L1)(2)](2+) where M = Zn, Cd, Cu. Ligand L2 = tris(nicotinoyl-N-oxide)cyclotriguaiacylene forms a 2-D coordination polymer with 4(4) (sql) grid topology in complexes {[M(L2)(2)(DMF)(2)]·2ClO(4)·8(DMF)}(∞) M = Cd or Cu, DMF = N,N'-dimethylformamide, and a double-linked chain structure in {[Co(L2)(2)(DMF)(2)]·2NO(3)·4(DMF)·H(2)O}(∞), and both types of structure feature hand-shake self-inclusion motifs either within or between the polymers.

Allosteric effects in a ditopic ligand containing bipyridine and tetra-aza-crown donor units.

Artificial allosterism: A ditopic ligand, which contains both bipyridine and tetra-aza-crown binding sites, coordinates one Cu(II) through all four N-donors of the tetradentate aza-crown unit. Reaction at the bipyridine site with another Cu(II) allosterically changes the aza-crown from being a tetradentate to a tridentate N-donor unit, a change in coordination mode that causes the successive binding of two Cu(II) ions to proceed with severe negative cooperativity (see scheme).

Urinary pharmacokinetic methodology to determine the relative lung bioavailability of inhaled beclometasone dipropionate.

Aim: Urinary pharmacokinetic methods have been identified to determine the relative lung and systemic bioavailability after an inhalation. We have extended this methodology to inhaled beclometasone dipropionate (BDP).

Method: Ethics Committee approval was obtained and all subjects gave consent.

Probing solution behaviour of metallosupramolecular complexes using pyrene fluorescence.

A new method for assessing the topology of metallosupramolecular assemblies using pyrene-appended ligands is reported. Two potentially tetradentate ligands containing one (L(1)) and two (L(2)) terminal pyrene moieties were synthesised and their complexes with Cu(+) and Cd(2+) were characterised. Photophysical measurements demonstrate that in [Cu(2)(L(1))(2)](2+), [CdL(1)](2+) and [Cu(2)(L(2))(2)](2+) the emission spectra are dominated by monomeric emission but in the cadmium complex of L(2) (where the pyrene units are in close proximity) a quenching of the luminescence coupled with weak emission at 540 nm is indicative of excimer formation.

Diastereoselective assembly of pentanuclear circular helicates.

Reaction of a ligand which contains two N-donor and O-donor tridentate domains separated by a 1,3-phenylene spacer unit with Zn(2+) ions results in a pentanuclear circular helicate [Zn(5)(L)(5)](10+) and this structure persists in both the solid and solution state. The formation of this high nuclearity species is governed by unfavourable steric interactions between the phenyl units which destabilize the simple linear helicate. Incorporation of enantiopure units within the ligand strand controls the diastereoselectivity with up to 80% d.

M3L2 metallo-cryptophanes: [2]catenane and simple cages.

Crystalline M(3)L(2) complexes with either single cage or triply interlocking [2]catenane chiral structures are formed the self-assembly of host-like ligands with transition metals.

Ag(I) organometallic coordination polymers and capsule with tris-allyl cyclotriveratrylene derivatives.

Tris-allyl-cyclotriguaiacylene combines with silver salts to give a range of crystalline network structures and one discrete complex. A number of different coordination modes are found within the complexes including η(2)-allyl, aryl, and OR groups binding to Ag(I). AgSbF(6) gives two types of three-dimensional (3-D) coordination polymer with unusual topologies, along with a discrete Ag(2)L(2) capsule dependent on reaction stoichiometry and reaction conditions.

Luminescent probes based on water-soluble, dual-emissive lanthanide complexes: metal ion-induced modulation of near-IR emission.

Responsive lanthanide complexes demonstrate differentiated modulated luminescence output upon exposure to metal di-cations in aqueous solution.

Controlling the formation of metallosupramolecular assemblies by metal ionic radii.

The formation of either dinuclear double-stranded or pentanuclear circular helicates from a ligand containing two tridentate domains separated by a phenylene unit can be controlled by inter-ligand steric interactions which themselves are governed by the size of the metal ion.

Responsive, di-metallic lanthanide complexes of a piperazine-bridged bis-macrocyclic ligand: modulation of visible luminescence and proton relaxivity.

The synthesis of a new functionalised bis-macrocyclic ligand (L1) is described together with the corresponding Ln(III) complexes, Ln(2)- (Ln = Gd(III), Eu(III)). Phosphorescence measurements on Gd(2)- at 77 K allowed the ligand-centred triplet state ((3)pi-pi*) to be estimated at ca. 28500 cm(-1).

Host-guest influence on metallo-supramolecular assemblies with a cyclotriveratrylene-type ligand.

The structure-directing effect of guest binding in metallo-supramolecular assemblies of host-type ligands is observed with a 2-D coordination polymer formed between Cd(OAc)(2) and tris(4-pyridylmethylamino)cyclotriguaiacylene in the presence of the globular guest o-carborane, and a trinuclear Cd(II) complex formed in solution in the absence of the bulky guest.