Cohort profile: a large EHR-based cohort with linked pharmacy refill and neighbourhood social determinants of health data to assess heart failure medication adherence.

Purpose: Clinic-based or community-based interventions can improve adherence to guideline-directed medication therapies (GDMTs) among patients with heart failure (HF). However, opportunities for such interventions are frequently missed, as providers may be unable to recognise risk patterns for medication non-adherence. Machine learning algorithms can help in identifying patients with high likelihood of non-adherence.

Leveraging Electronic Health Record Technology and Team Care to Address Medication Adherence: Protocol for a Cluster Randomized Controlled Trial.

Background: Low medication adherence is a common cause of high blood pressure but is often unrecognized in clinical practice. Electronic data linkages between electronic health records (EHRs) and pharmacies offer the opportunity to identify low medication adherence, which can be used for interventions at the point of care. We developed a multicomponent intervention that uses linked EHR and pharmacy data to automatically identify patients with elevated blood pressure and low medication adherence.

-Fluoro-Thiol Reaction on Anchor Layers Grafted from an Aryldiazonium Salt: A Tool for Surface Functionalization with Thiols.

A new coupling reaction, the -fluoro-thiol (PFT) reaction, activated by base at room temperature, is reported for carbon surface functionalization. 4-Nitrothiophenol (4-NTP) and (3-nitrobenzyl)mercaptan (3-NBM) were coupled to pentafluorophenyl (F-Ph) anchor layers grafted from the aryldiazonium ion formed . The relative yields of the PFT reactions, estimated from the electrochemical responses of coupled nitrophenyl (NP) and nitrobenzyl (NB) groups, depended on the nucleophilicity of the thiolate and the strength of the base.

Building Tailored Interfaces through Covalent Coupling Reactions at Layers Grafted from Aryldiazonium Salts.

Aryldiazonium ions are widely used reagents for surface modification. Attractive aspects of their use include wide substrate compatibility (ranging from plastics to carbons to metals and metal oxides), formation of stable covalent bonding to the substrate, simplicity of modification methods that are compatible with organic and aqueous solvents, and the commercial availability of many aniline precursors with a straightforward conversion to the active reagent. Importantly, the strong bonding of the modifying layer to the surface makes the method ideally suited to further on-surface (postfunctionalization) chemistry.

Accessing a Long-Lived LC State in a Ruthenium(II) Phenanthroline Complex with Appended Aromatic Groups.

The photophysical properties of a series of heteroleptic Ru(II) complexes of the form [Ru(phen)(phen-5,6-R)], where phen = 1,10-phenanthroline and R = phenyl (Ph), --butylbenzene (-Ph-tBu), -methoxybenzene (-Ph-OMe), and 2-naphthalene (2-naph), have been measured. Variation of the R group does not greatly perturb the electronic properties of the ground state, which were explored with electronic absorption and resonance Raman spectroscopy and are akin to those of the archetypal parent complex [Ru(phen)]. All complexes were shown to possess emissive MLCT states, characterized through transient absorption and emission spectroscopy.

A study of di(amino)stibines with terminal Sb(iii) hydrogen-ligands by X-ray- and neutron-diffraction.

The bis(amidodimethyl)disiloxane ligands [O{SiMe2NR}2]2- (R = 2,6-Me2C6H3 (Ar') and 2,6-iPr2C6H3 (Ar), abbreviated [NONR]2-, are a stable support for Sb(iii) complexes of general formula Sb(NONR)X (X = Cl, H). The compounds are monomeric in the solid-state, with bidentate N,N'-coordination of the [NONR]2- and terminal chloride/hydrogen-ligands. Sb(NONAr')H was analyzed by single-crystal neutron diffraction, giving the first accurate parameters for the Sb-H bond to an antimony(iii) centre.

Predicting the Outcome of Photocyclisation Reactions: A Joint Experimental and Computational Investigation.

Photochemical oxidative cyclodehydrogenation reactions are a versatile class of aromatic ring-forming reactions. They are tolerant to functional group substitution and heteroatom inclusion, so can be used to form a diverse range of extended polyaromatic systems by fusing existing ring substituents. However, despite their undoubted synthetic utility, there are no existing models-computational or heuristic-that predict the outcome of photocyclisation reactions across all possible classes of reactants.

Intramolecular Metal⋅⋅⋅π-Arene Interactions in Neutral and Cationic Main Group Compounds.

The role of intramolecular metal⋅⋅⋅π-arene interactions has been investigated in the solid-state structures of a series of main group compounds supported by the bulky amide ligands, [N( Ar )(SiR )] ( Ar =2,6-(CHPh ) -4-tBuC H , R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the SiPh substituent is able to be involved in stabilizing the electrophilic metal. These group 1 metal compounds served as ligand transfer reagents to access a series of bismuth(III) halides.

MicroRNA and transcriptome analysis in periocular Sebaceous Gland Carcinoma.

Sebaceous gland carcinoma (SGC) is a rare, but life-threatening condition with a predilection for the periocular region. Eyelid SGC can be broadly categorised into two subtypes, namely either nodular or pagetoid with the latter being more aggressive and requiring radical excision to save life. We have identified key altered microRNAs (miRNA) involved in SGC shared by both subtypes, hsa-miR-34a-5p and hsa-miR-16-5p.

Indyllithium and the Indyl Anion [InL] : Heavy Analogues of N-Heterocyclic Carbenes.

Reduction of the indate complex In(NON )(μ-Cl) Li(OEt ) (NON =[O(SiMe NAr) ] ; Ar=2,6-iPr C H ) with sodium generates the In diindane species [In(NON )] . Further reduction with a mixture of potassium and [2.2.

Catalytic oxidative coupling promoted by bismuth TEMPOxide complexes.

Bismuth(iii) TEMPOxide compounds have been synthesized from the coupling of Bi(ii) species with the TEMPO˙ radical. The steric profile of the supporting bis(amido)disiloxane ligand promotes different fluxional behaviour in solution, and DFT calculations suggest variation in the Bi-O bond character. These compounds are active catalysts for oxidative coupling of TEMPO and silane substrates, believed to proceed via metathesis of Bi-O and Si-H bonds followed by decomposition of bismuth-hydride intermediate species.

Carbodiimides as catalysts for the reduction of a cadmium hydride complex.

A rare terminal cadmium hydride complex [(BDI)CdH] (BDI = [{N(2,6-iPrCH)C(Me)}CH]) has been synthesised from [(BDI)CdCl] and LiEtBH. The hydride can be reduced to the cadmium(i) dimer, [(BDI)CdCd(BDI)] upon treatment with a catalytic amount of diisopropyl- or dicyclohexylcarbodiimide.

Photochemical and oxidative cyclisation of tetraphenylpyrroles.

The photochemical and oxidative cyclodehydrogenation reactions of tetraphenylpyrroles act in a complementary fashion for the cyclisation of N-ethyl and N-benzyl derivatives. In the case of the former, a doubly cyclised product was isolated from cyclisation with solid FeCl, while the latter gives a rearranged 3H-pyrrole upon irradiation.

Bismuth(III) Complex of the [S] Radical Anion: Dimer Formation via Pancake Bonds.

Reaction of bismuth(II) compounds with sulfur gives mixtures of [Bi(NON)](μ-S) (NON = [O(SiMeNR)]). Examples for n = 1 and 3 have been crystallographically verified for R = 2,6-iPrCH (Dipp) and R = tBu, and the pentasulfide (n = 5) for R = Dipp. The corresponding product from reaction with the new Bi(II) radical Bi(NON) (Ar = CH(CHPh)-tBu-2,6,4) exists as the dimer [Bi(NON)(S)], with π*(SOMO)-π*(SOMO) interactions linking the sulfur chains through trans-antarafacial pancake bonds.

Neutral and cationic bismuth compounds supported by bis(amidodimethyl)disiloxane ligands.

Bis(amidodimethyl)disiloxane ligands derived from O{SiMeN(H)R} (abbreviated as (NON)H) are a stable support for neutral and cationic bismuth compounds. Attempts to extend the series Bi(NON)Cl (R = Ar = 2,6-iPrCH; R = tBu) to include compounds where R = Ar' = 2,6-MeCH were complicated by concomitant formation of the bimetallic compound {Bi(NON)}(μ-NON). Compounds containing [Bi(NON)] cations were obtained from reactions with group 13 chlorides MCl (M = Al, Ga).

Hydrophosphination-type reactivity promoted by bismuth phosphanides: scope and limitations.

Phenyl isocyanate inserts into the Bi-P bond of the terminal phosphanide Bi(NON)(PCy) (NON = [O(SiMeNAr)] Ar = 2,6-iPrCH) to afford the κN,O-phosphanylcarboxamidate complex. Liberation of the hydrophosphination product from the metal is achieved by reaction with HPPh. The diphenylphosphanide product, Bi(NON)(PPh), is however unstable and decomposes to generate reduced species, preventing catalytic turnover.

Bi-P Bond Homolysis as a Route to Reduced Bismuth Compounds and Reversible Activation of P.

Bismuth diphenylphosphanides Bi(NON )(PPh ) (NON =[O(SiMe NR) ], R=tBu, 2,6-iPr C H , Aryl) undergo facile decomposition via single-electron processes to form reduced Bi and P species. The corresponding derivatives Bi(NON )(PCy ) are stable. Reaction of the isolated Bi radical Bi(NON ) with white phosphorus (P ) proceeds with the reversible and selective activation of a single P-P bond to afford the bimetallic μ,η -bicyclo[1.

Diels-Alder Reaction of Anthranilic Acids: A Versatile Route to Dense Monolayers on Flat Edge and Basal Plane Graphitic Carbon Substrates.

Methods that reliably yield monolayers of covalently anchored modifiers on graphene and other planar graphitic materials are in demand. Covalently bonded groups can add functionality to graphitic carbon for applications ranging from sensing to supercapacitors and can tune the electronic and optical properties of graphene. Limiting modification to a monolayer gives a layer with well-defined concentration and thickness providing a minimum barrier to charge transfer.

(15)N NMR Spectroscopy, X-ray and Neutron Diffraction, Quantum-Chemical Calculations, and UV/vis-Spectrophotometric Titrations as Complementary Techniques for the Analysis of Pyridine-Supported Bicyclic Guanidine Superbases.

Pyridine substituted with one and two bicyclic guanidine groups has been studied as a potential source of superbases. 2-{hpp}C5H4N (I) and 2,6-{hpp}2C5H3N (II) (hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) were protonated using [HNEt3][BPh4] to afford [I-H][BPh4] (1a), [II-H][BPh4] (2), and [II-H2][BPh4]2 (3). Solution-state (1)H and (15)N NMR spectroscopy shows a symmetrical cation in 2, indicating a facile proton-exchange process in solution.

Mesenchymal Stem Cell-Like Properties of Orbital Fibroblasts in Graves' Orbitopathy.

Purpose: Graves' orbitopathy (GO) is a sight-threatening autoimmune disorder causing extraocular muscle fibrosis, upper lid retraction and eye bulging due to orbital fat expansion. These clinical features are mediated by aspects of orbital fibroblasts differentiation, including adipogenesis and fibrosis. Our previous work suggested that this dual phenotype might be a manifestation of mixed cell populations, partially linked to the expression of mesenchymal stem cell (MSC) marker CD90.

Isolation and Characterization of a Bismuth(II) Radical.

More than 80 years after Paneth's report of dimethyl bismuth, the first monomeric Bi(II) radical that is stable in the solid state has been isolated and characterized. Reduction of the diamidobismuth(III) chloride Bi(NON(Ar))Cl (NON(Ar)=[O(SiMe2NAr)2](2-); Ar=2,6-iPr2C6H3) with magnesium affords the Bi(II) radical ˙Bi(NON(Ar)). X-ray crystallographic measurements are consistent with a two-coordinate bismuth in the +2 oxidation state with no short intermolecular contacts, and solid-state SQUID magnetic measurements indicate a paramagnetic compound with a single unpaired electron.

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid.

The synthesis, structural and thermal characterisation of a number of coordination complexes featuring the N,O-heteroditopic ligand 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate, HL are reported. The reaction of H2L with cobalt(II) and nickel(II) nitrates at room temperature in basic DMF/H2O solution gave discrete mononuclear coordination complexes with the general formula {[M(HL)2(H2O)4]·2DMF} (M = Co (1), Ni (2)), whereas the reaction with zinc(II) nitrate gave [Zn(HL)2]∞, 3, a coordination polymer with distorted diamondoid topology and fourfold interpenetration. Coordination about the tetrahedral Zn(II) nodes in 3 are furnished by two pyrazolyl nitrogen atoms and two carboxylate oxygen atoms to give a mixed N2O2 donor set.

Variation of guest selectivity within [Fe4L4](8+) tetrahedral cages through subtle modification of the face-capping ligand.

We report here the host-guest behaviour of two isoelectronic [Fe4L4](8+) tetrahedral cages that differ only in the nature of their face-capping ligand and possess either triazine (L1) or benzene (L2) cores. Crystallography reveals these hosts to be flexible and adaptable, while NMR spectroscopy shows them to be selective and discriminating in their host-guest behaviour.

Conformational control of the self-assembly of triple helicates and [2 × 2]-grids from zinc(II) and 3,6-di(2-pyridyl)pyridazine based ligands.

The reaction of symmetrical ligands based on 3,6-di(2-pyridyl)pyridazine () with carbocyclic rings fused to the pyridazine ring; 7,10-di(2-pyridyl)-8,9-diazafluoranthene (), 1,4-di(2-pyridyl)-6,7-dihydro-5H-cyclopenta[d]pyridazine (), 1,4-di(2-pyridyl)-5,6,7,8-tetrahydrophthalazine (), 1,4-di(2-pyridyl)-6,7,8,9-tetrahydro-5H-cyclohepta[d]pyridazine () in reactions with zinc perchlorate gave a series of complexes (). Characterisation of these using single crystal X-ray structure determination showed that less sterically hindered and gave saturated triple helicates ( and , respectively), while [2 × 2]-grids were formed with more sterically hindered ligands ( from and from ), or if methanol (rather than acetonitrile) was used as the reaction solvent with (). The most sterically-hindered ligand formed a mononuclear complex ().

Independent adipogenic and contractile properties of fibroblasts in Graves' orbitopathy: an in vitro model for the evaluation of treatments.

Graves' orbitopathy (GO) is a disfiguring and sometimes blinding disease, characterised by inflammation and swelling of orbital tissues, with fibrosis and adipogenesis being predominant features. Little is known about the disease aetiology and the molecular mechanisms driving the phenotypic changes in orbital fibroblasts are unknown. Using fibroblasts isolated from the orbital fat of undiseased individuals or GO patients, we have established a novel in vitro model to evaluate the dual profile of GO cells in a three-dimensional collagen matrix; this pseudo-physiological 3D environment allows measurement of their contractile and adipogenic properties.