Single-Crystal X-ray Diffraction Studies of Solvated Crystals of C Reveal the Intermolecular Interactions between the Component Molecules.

The solid-state structures of seven solvates of C (C·4tetrachloroethylene, C·2tetrachloroethylene, C·3benzene, C· n-pentane, C·diethyl ether, C·chlorobenzene, and C·benzene·dichloromethane) were determined by single-crystal X-ray diffraction at low temperature. At 90 K, the fullerene and solvate components are generally well-ordered and do not show the orientational disorder that plagues similar structures determined at room temperature. Interactions between the solvate molecules and the fullerene and between adjacent C molecules were examined and analyzed.

Crystallization and interconversions of vapor-sensitive, luminescent polymorphs of [(C6H11NC)2Au(I)](AsF6) and [(C6H11NC)2Au(I)](PF6).

The remarkable, vapor-induced transformation of the yellow polymorphs of [(C(6)H(11)NC)(2)Au(I)](AsF(6)) and [(C(6)H(11)NC)(2)Au(I)](PF(6)) into the colorless forms are reported along with related studies of the crystallization of these polymorphs. Although the interconversion of these polymorphs is produced by vapor exposure, molecules of the vapor are not incorporated into the crystals. Thus, our observations may have broad implications regarding the formation and persistence of other crystal polymorphs where issues of stability and reproducibility of formation exist.

Prochelators triggered by hydrogen peroxide provide hexadentate iron coordination to impede oxidative stress.

Prochelators are agents that have little affinity for metal ions until they undergo a chemical conversion. Three new aryl boronate prochelators are presented that are responsive to hydrogen peroxide to provide hexadentate ligands for chelating metal ions. TRENBSIM (tris[(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzylidene)-2-aminoethyl]amine), TRENBSAM (tris[(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoyl)-2-aminoethyl]amine), and TB (tris[(2-boronic acid-benzyl)2-aminoethyl]amine) convert to TRENSIM (tris[(salicylideneamino)ethyl]amine), TRENSAM (tris[(2-hydroxybenzoyl)-2-aminoethyl]amine), and TS (tris[2-hydroxybenzyl)2-aminoethyl]amine), respectively.

Selective activation of p53-mediated tumour suppression in high-grade tumours.

Non-small cell lung carcinoma (NSCLC) is the leading cause of cancer-related death worldwide, with an overall 5-year survival rate of only 10-15%. Deregulation of the Ras pathway is a frequent hallmark of NSCLC, often through mutations that directly activate Kras. p53 is also frequently inactivated in NSCLC and, because oncogenic Ras can be a potent trigger of p53 (ref.

Blue or green glowing crystals of the cation [Au{C(NHMe)2}2]+. Structural effects of anions, hydrogen bonding, and solvate molecules on the luminescence of a two-coordinate gold(I) carbene complex.

Depending upon the crystallization conditions, [Au{C(NHMe) 2} 2](AsF 6) forms colorless crystals that display a blue or green luminescence. The difference involves the type of solvate molecule that is incorporated into the crystal and the structure of the chains of cations that are formed upon crystallization. The crystallographically determined structures of blue-glowing [Au{C(NHMe) 2} 2](AsF 6).

Counterions influence reactivity of metal ions with cysteinyldopa model compounds.

Cysteinyldopas are naturally occurring conjugates of cysteine and dopa (3,4-dihydroxy-l-phenylalanine) that are precursors to red pheomelanin pigments. Metal ions are known to influence pheomelanogenesis in vitro and may be regulatory factors in vivo. Cydo (3-[(2-amino-ethyl)sulfanyl]-4,6-di-tert-butylbenzene-1,2-diol) and CarboxyCydo (2-amino-3-(4,6-di-tert-butyl-2,3-dihydroxyphenylsulfanyl)-propionic acid) are model compounds of cysteinyldopa that retain its metal-binding functionalities but cannot polymerize due to the presence of blocking tert-butyl groups.

Modifications of boronic ester pro-chelators triggered by hydrogen peroxide tune reactivity to inhibit metal-promoted oxidative stress.

Several new analogs of salicylaldehyde isonicotinoyl hydrazone (SIH) and salicylaldehyde benzoyl hydrazone (SBH) that contain an aryl boronic ester (BSIH, BSBH) or acid (BASIH) in place of an aryl hydroxide have been synthesized and characterized as masked metal ion chelators. These pro-chelators show negligible interaction with iron(III), although the boronic acid versions exhibit some interaction with copper(II), zinc(II) and nickel(II). Hydrogen peroxide oxidizes the aryl boronate to phenol, thus converting the pro-chelators to tridentate ligands with high affinity metal binding properties.

A pro-chelator triggered by hydrogen peroxide inhibits iron-promoted hydroxyl radical formation.

The synthesis and structural characterization of a new pro-chelating agent, isonicotinic acid [2-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzylidene]-hydrazide (BSIH), are presented. BSIH only weakly interacts with iron unless hydrogen peroxide (H2O2) is present to remove the boronic ester protecting group to reveal a phenol that is a key metal-binding group of tridentate salicylaldehyde isonicotinoyl hydrazone (SIH). BSIH prevents deoxyribose degradation caused by hydroxyl radicals that are generated from H2O2 and redox-active iron by sequestering Fe3+ and preventing iron-promoted hydroxyl radical formation.

Synthesis and characterization of copper(II) complexes of cysteinyldopa and benzothiazine model ligands related to pheomelanin.

A new cysteinyldopa model ligand Cydo {3-[(2-aminoethyl)sulfanyl]-4,6-di-tert-butylbenzene-1,2-diol} was prepared and its reactivity with Cu(II) explored. Under anaerobic conditions, tetranuclear [Cu4(Cydo)4] is isolated, but in the presence of O2, a benzothiazine intermediate accumulates that is trapped as the Cu(II) complex [Cu(zine)2]. Under slightly different reaction conditions, the benzothiazine further oxidizes to benzothiazole (zole).

A reversible polymorphic phase change which affects the luminescence and aurophilic interactions in the gold (I) cluster complex, [mu3-S(AuCNC7H13)3](SbF6).

Crystallographic examination of [mu3-S(AuCNC7H13)3](SbF6) shows that it undergoes a reversible phase change from orthorhombic to monoclinic upon cooling. At 190 K, the structure shows that two cations self-associate to form a pseudo-octahedral array of six gold atoms connected by both intra- and interionic aurophilic interactions. On cooling, the clusters become less symmetric, and in one, the interionic Au.