Synthesis of bombesin-functionalized iron oxide nanoparticles and their specific uptake in prostate cancer cells

The imaging of molecular markers associated with disease offers the possibility for earlier detection and improved treatment monitoring. Receptors for gastrin-releasing peptide are overexpressed on prostate cancer cells offering a promising imaging target, and analogs of bombesin, an amphibian tetradecapeptide have been previously demonstrated to target these receptors. Therefore, the pan-bombesin analog [β-Ala11, Phe13, Nle14]bombesin-(7–14) was conjugated through a linker to dye-functionalized superparamagnetic iron oxide nanoparticles for the development of a new potential magnetic resonance imaging probe. The peptide was conjugated via click chemistry, demonstrating a complementary alternative methodology to conventional peptide-nanoparticle conjugation strategies. The peptide-functionalized nanoparticles were then demonstrated to be selectively taken up by PC-3 prostate cancer cells relative to unfunctionalized nanoparticles and this uptake was inhibited by the presence of free peptide, confirming the specificity of the interaction. This study suggests that these nanoparticles have the potential to serve as magnetic resonance imaging probes for the detection of prostate cancer.     

Synthesis and characterisation of dimeric eight-coordinate lanthanide(III) complexes of a macrocyclic tribenzylphosphinate ligand

The macrocyclic ligand 1,4,7,10-tetraazacyclododecane-1,4,7-triyl(methylenebenzyl-phosphinic acid) H3L3, has been prepared and its complexes with Eu, Gd and Tb(III) studied by NMR, relaxometry, luminescence and single crystal X-ray crystallography. In solution and in the crystal, the complexes have eight-coordinate metal centres with bridging phosphinate groups linking the two twisted square antiprismatic coordination polyhedra. A single stereoisomer crystallises from solution with an RRR and SSS configuration at the P centres in each sub-unit. The relaxivity of [GdL3]2 is low (1.9 mM-1 s-1, 298 K, 20 MHz), consistent with the absence of any proximate water molecules. The terbium dimer possesses a relatively long excited state lifetime (2.47 ms, 298 K).     

Ortho effect in the Bergman cyclization: electronic and steric effects in hydrogen abstraction by 1-substituted naphthalene 5,8-diradicals

We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an sigma framework.     

Functional Nickel Oxide Nanostructures for Ethanol Oxidation in Alkaline Media

Nickel oxide (NiO) nanostructures are employed in the basic medium for the oxidation of ethanol. A variety of NiO nanostructures are synthesized by wet chemical growth method, using different hydroxide (OH^?) ion sources, particularly from ammonia, hexamethylenetetramine, urea and sodium hydroxide. The use of urea as (OH^?) ion source results in flower‐like NiO structures composed by extremely thin nanowalls (thickness lower than 10 nm,), which demonstrated to be the most active for ethanol oxidation. All the samples exhibit NiO cubic phase, and no other impurity was detected. The cyclic voltammetry (CV) curves of NiO nanostructures were found linear over the concentration range 0.1–3.5 mM (R²=0.99) of ethanol, with the limit of detection estimated to be 0.013 mM for ethanol. The NiO nanostructures exhibit a selective signal towards ethanol oxidation in the presence of different members of alcohol family. The proposed NiO nanostructures showed a significant practicality for the reproducible and sensitive determination of ethanol from brandy, whisky, mixture of brandy and rum, and vodka samples. The nanomaterial was used as a surface modifying agent for the glassy carbon electrode and it showed a stable electro‐oxidation activity for the ethanol for 16 days. These findings indicate that the presented NiO nanomaterial can be applied in place of noble metals for ethanol sensing and other environmental applications (like fuel cells).     

Radical Cyclisation of α‐Halo Aluminium Acetals: A Mechanistic Study

α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature ¹³C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al₂O₂ ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences.     

Asymmetric synthesis of novel spirocycles via a chiral phosphoric acid catalyzed desymmetrization

A straightforward method for the asymmetric preparation of novel lactone and lactam spirocycles is described. An initial desymmetrization via a chiral Brønsted acid yields enantioenriched lactones which readily undergo a second cyclization to give the desired spirocycle.