A Novel Antimicrobial Hydrogel for the Management of Periodontal Diseases.

Objectives: This study aimed to synthesise a drug-delivery system based on a porous polymer hydrogel, with antimicrobial properties against Porphyromonas gingivalis and potential to be used in tissue regeneration.

Material And Methods: 2-Hydroxyethyl methacrylate monomers were polymerised using thermal and photoactivation in the presence of silver nitrate (AgNO) and/or chlorhexidine digluconate. Poly-2-hydroxyethyl methacrylate (pHEMA) hydrogels containing silver nanoparticles (AgNPs) and/or 0.

Maraviroc Prevents HCC Development by Suppressing Macrophages and the Liver Progenitor Cell Response in a Murine Chronic Liver Disease Model.

Maraviroc (MVC), a CCR5 antagonist, reduces liver fibrosis, injury and tumour burden in mice fed a hepatocarcinogenic diet, suggesting it has potential as a cancer therapeutic. We investigated the effect of MVC on liver progenitor cells (LPCs) and macrophages as both have a role in hepatocarcinogenesis. Mice were fed the hepatocarcinogenic choline-deficient, ethionine-supplemented diet (CDE) ± MVC, and immunohistochemistry, RNA and protein expression were used to determine LPC and macrophage abundance, migration and related molecular mechanisms.

Ca detection utilising AlGaN/GaN transistors with ion-selective polymer membranes.

We demonstrate highly selective and sensitive potentiometric ion sensors for calcium ion detection, operated without the use of a reference electrode. The sensors consist of AlGaN/GaN heterostructure-based transistor devices with chemical functionalisation of the gate area using poly (vinylchloride)-based (PVC) membranes having high selectivity towards calcium ions, Ca. The sensors exhibited stable and rapid responses when introduced to various concentrations of Ca.

Stable Au complexes with four N-heterocyclic carbene groups can be prepared in high yield directly from KAuCl.

Gold(iii) N-heterocyclic carbene (NHC) complexes of form [Au(NHC)Cl]Cl were synthesized by reaction of KAuCl with bis- and tetrakis(imidazolium) salts in the presence of a mild base. Treatment of these complexes with KPF afforded four-coordinate Au complexes of form [Au(NHC)](PF). X-Ray crystallography showed the [Au(NHC)] cations in the hexafluorophosphate salts to have a square planar Au(NHC) moiety [AuC 2.

Dinuclear Au(i) N-heterocyclic carbene complexes derived from unsymmetrical azolium cyclophane salts: potential probes for live cell imaging applications.

We have synthesized a new series of azolium cyclophanes and used them as precursors of inherently luminescent dinuclear Au(i)-N-heterocyclic carbene (NHC) complexes. The azolium cyclophanes contained two azolium groups (either imidazolium or benzimidazolium), an o-xylyl group, and an alkyl linker chain (either C2, C3 or C4). All of the azolium cyclophanes were characterised by X-ray diffraction studies and VT NMR studies, and all were fluxional in solution on the NMR timescale.

Pore size dynamics in interpenetrated metal organic frameworks for selective sensing of aromatic compounds.

The two-fold interpenetrated metal-organic framework, [Zn2(bdc)2(dpNDI)]n (bdc=1,4-benzenedicarboxylate, dpNDI=N'N'-di(4-pyridyl)-1,4,5,8-naphthalenediimide) can undergo structural re-arrangement upon adsorption of chemical species changing its pore structure. For a competitive binding process with multiple analytes of different sizes and geometries, the interpenetrated framework will adopt a conformation to maximize the overall binding interactions. In this study, we show for binary mixtures that there is a high selectivity for the larger methylated aromatic compounds, toluene and p-xylene, over the small non-methylated benzene.

Improving the cellular invasion into PHEMA sponges by incorporation of the RGD peptide ligand: the use of copolymerization as a means to functionalize PHEMA sponges.

A monomer that contained the RGD ligand motif was synthesized and copolymerized with 2-hydroxyethyl methacrylate using polymerization-induced phase separation methods to form poly(2-hydroxyethyl methacrylate)-based hydrogel sponges. The sponges had morphologies of aggregated polymer droplets and interconnected pores, the pores having dimensions in the order of 10 μm typical of PHEMA sponges. RGD-containing moieties appeared to be evenly distributed through the polymer droplets.

Enhanced deep-blue emission from Pt(II) complexes bound to 2-pyridyltetrazolate and an ortho-xylene-linked bis(NHC)cyclophane.

The coordination of 2-pyridyltetrazolate and ortho-xylene-linked bis(NHC)cyclophane to Pt(II) yielded a novel complex characterised by enhanced pure deep-blue emission, whose intensity can be modulated via methylation of the tetrazole ring.

Biodegradation of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly{(2-hydroxyethyl methacrylate)-co-[poly(ethylene glycol) methyl ether methacrylate]} hydrogels containing peptide-based cross-linking agents.

PHEMA-peptide and P[HEMA-co-(MeO-PEGMA)]-peptide conjugate hydrogels [where PHEMA = poly(2-hydroxyethyl methacrylate; PEGMA = poly(ethylene glycol) methacrylate] were readily prepared via photoinitiated free-radical polymerization in water. The PHEMA-peptide hydrogels were opaque and had a heterogeneous morphology of interconnected polymer droplets, characteristic of polymers that separate from the aqueous phase during the polymerization experiment. The P[HEMA-co-(MeO-PEGMA)]-peptide conjugates were transparent gels with a homogeneous morphology when formed in water, but when formed in aqueous NaCl solutions the P[HEMA-co-(MeO-PEGMA)]-peptide conjugates were also opaque and exhibited the heterogeneous morphology of interconnected polymer droplets.

Palladium complexes of o-xylyl-linked alkoxybenzimidazolin-2-ylidenes: interesting structural conformations and application as pre-catalysts.

New PdBr(2)-bis(N-heterocyclic carbene) complexes derived from 4,7-dibutoxybenzimidazole and 5,6-dibutoxybenzimidazole have been synthesized and structurally and spectroscopically characterized. The complexes show much greater solubility compared to the parent complex derived from benzimidazole, and interesting structural characteristics dependent on the position of the butoxy substituents. The complexes display high activities in the coupling of aryl iodides in the Mizoroki-Heck reaction and moderate activities in the Suzuki-Miyaura coupling of inactivated aryl bromides at low catalyst loadings, although activity differences between pre-catalysts has been observed.

A new binding geometry for an ortho-xylylene-linked bis(NHC)cyclophane: a ruthenium(II) complex with a chelating (eta(1)-NHC)2:eta(6)-arene ligand.

Using two different reaction procedures, a Ru(II) complex has been isolated that contains an ortho-xylylene-linked bis(NHC)cyclophane (NHC = N-heterocyclic carbene) that binds to the Ru centre through two carbene carbons and one of the arene rings in an eta(6)-mode.

Octapi interactions: self-assembly of a Pd-based [2]catenane driven by eightfold pi interactions.

An unprecedented 2.5 nm array of pi interactions between eight aromatic rings drives the formation of a [2]catenane. Disruption of this array through the use of longer ligands results in the formation of only single, uncatenated rings.

Azolium-linked cyclophanes: effects of structure, solvent, and counteranions on solution conformation behavior.

This paper describes the synthesis, structural characterization, and solution behavior of some xylyl-linked imidazolium and benzimidazolium cyclophanes decorated with alkyl or alkoxy groups. The addition of alkyl/alkoxy chains to the cyclophanes allows for studies in chlorinated solvents, whereas previous solution studies of azolium cyclophanes have generally required highly polar solvents. The azolium cyclophanes may exist in a syn/syn conformation (azolium rings mutually syn, arene rings mutually syn) or a syn/anti conformation (azolium rings mutually syn, arene rings mutually anti).

Mitochondria-targeted chemotherapeutics: the rational design of gold(I) N-heterocyclic carbene complexes that are selectively toxic to cancer cells and target protein selenols in preference to thiols.

A family of lipophilic, cationic Au(I) complexes of N-heterocyclic carbenes (NHCs) have been designed as new mitochondria-targeted antitumor agents that combine both selective mitochondrial accumulation and selective thioredoxin reductase inhibition properties within a single molecule. Two-step ligand exchange reactions with cysteine (Cys) and selenocysteine (Sec) occur with release of the NHC ligands. At physiological pH the rate constants for the reactions with Sec are 20- to 80-fold higher than those with Cys.

Bioenergetic differences selectively sensitize tumorigenic liver progenitor cells to a new gold(I) compound.

A hallmark of cancer cells is their ability to evade apoptosis and mitochondria play a critical role in this process. Delineating mitochondrial differences between normal and cancer cells has proven challenging due to the lack of matched cell lines. Here, we compare two matched liver progenitor cell (LPC) lines, one non-tumorigenic [p53-immortalized liver (PIL) 4] and the other tumorigenic (PIL2).

Cationic, linear Au(I) N-heterocyclic carbene complexes: synthesis, structure and anti-mitochondrial activity.

Six linear, two-coordinate cationic Au(I) N-heterocyclic carbene complexes of the form [(R2Im)2Au]+ (R = Me 1, Me, Et 2, i-Pr 3, n-Bu 4, t-Bu 5 and Cy 6) have been prepared by the reaction of two equivalents of the appropriate dialkylimidazol-2-ylidene (R2Im) with (Me2S)AuCl in dmf. Single crystal structural studies for 1.PF6, 2.

Synthetic, structural and spectroscopic studies of (pseudo)halo(1,3-di-tert-butylimidazol-2-ylidine)gold complexes.

A series of (pseudo)halo(1,3-di-tert-butylimidazol-2-ylidine)gold complexes [(But2Im)AuX](X = Cl, Br, I, CN, N3, NCO, SCN, SeCN, ONO2, OCOCH3, CH3) have been synthesized and characterised spectroscopically and structurally. 13C NMR chemical shifts for the carbene carbon vary widely with differing ancillary anion, correlating well with the sigma-donor ability of the latter and with the M-C(carbene) bond distance. These results reinforce the notion that N-heterocyclic carbene ligands are primarily sigma-donor ligands with little pi-acceptor ability.

Dinuclear N-heterocyclic carbene complexes of silver(I), derived from imidazolium-linked cyclophanes.

The synthesis of four new silver complexes of bidentate N-heterocyclic carbenes, derived from imidazolium-linked cyclophanes, has been achieved via a simple complexation reaction of the imidazolium-linked cyclophanes with the basic metal source Ag(2)O. The cyclophane structures contain two imidazolyl links between ortho-, meta- and mixed ortho/meta-substituted aromatic rings. The new silver carbene systems are thermally stable and have been characterised by NMR spectroscopy and X-ray crystallography.

Azolium-linked cyclophanes: a comprehensive examination of conformations by 1H NMR spectroscopy and structural studies.

The synthesis and characterization of a series of azolium-linked cyclophanes are reported. The cyclophanes consist of two azolium groups (17 examples) or three imidazolium groups (1 example) linked to two benzenoid units (benzene, naphthalene, p-xylene, mesitylene, 1,2,3,4- and 1,2,4,5-tetramethylbenzene, 2,6-pyridine, and p-tert-butylphenol) via methylene groups. Cyclophanes containing ortho-, meta-, and para-substitution patterns in the benzenoid units were examined.

Mitochondrial permeability transition induced by dinuclear gold(I)-carbene complexes: potential new antimitochondrial antitumour agents.

Seven dinuclear gold(I) complexes of bidentate N-heterocyclic carbene ligands have been evaluated for their ability to induce mitochondrial membrane permeabilisation (MMP) in isolated rat liver mitochondria. Six of the compounds, at concentrations of 10 microM, induced Ca(2+)-sensitive MMP as evidenced by mitochondrial swelling. In the absence of low concentrations of exogenous Ca(2+), the compounds were either inactive or their activity was significantly decreased.

Dinuclear gold(I) complexes of bridging bidentate carbene ligands: synthesis, structure and spectroscopic characterisation.

Eight dinuclear Au(i)-carbene complexes have been synthesized from various imidazolium-linked cyclophanes and related acyclic bis(imidazolium) salts, by treatment of the imidazolium salts with [Au(i)(SMe(2))Cl] in the presence of a carboxylate base. Single crystal structural studies showed that the Au(i)-carbene compounds contain dinuclear (AuL)(2) cations in which a pair of gold(i) centres are linked by a pair of bridging dicarbenoid ligands. Interestingly, the structural studies revealed short AuAu contacts of 3.

Oxidations of (R(3)tach)M(CO)(3) Complexes [M = Cr, Mo, W; R(3)tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R = t-Bu, Bn)]. Crystal Structures of (t-Bu(3)tach)MO(3).15H(2)O (M = Mo, W).

Stable Cr, Mo, and W complexes having a metal in oxidation state II, III, or VI, and possessing a facially coordinated 1,3,5-trialkyl-1,3,5-triazacyclohexane (R(3)tach) ligand, can be prepared by oxidation of (R(3)tach)M(CO)(3) with a variety of oxidizing agents. The reaction of the chromium or molybdenum complexes (R(3)tach)M(CO)(3) (M = Cr, R = Bn (benzyl), t-Bu and M = Mo, R = t-Bu) with bromine or thionyl chloride at reflux affords a series of monomeric M(III) trihalide complexes. More controlled oxidation of (t-Bu(3)tach)M(CO)(3) (M = Mo, W) with either bromine or iodine yields the 7-coordinate M(II) cations [(t-Bu(3)tach)M(CO)(3)X](+) (X = Br, I); protonation with trifluoromethanesulfonic acid affords the isolable [(t-Bu(3)tach)M(CO)(3)H](+) cations as their trifluoromethanesulfonate salts.