The Significant Influence of a Second Metal on the Antiproliferative Properties of the Complex [Ru(η6−C10H14)(Cl2)(dmoPTA)]

Complexes [Ru(η⁶−C₁₀H₁₄)(Cl₂)(HdmoPTA)](OSO₂CF₃) ( 1 ), [Ru(η⁶−C₁₀H₁₄)(Cl₂)(dmoPTA)] ( 2 ) and [Ru(η⁶−C₁₀H₁₄)(Cl₂)-μ-dmoPTA-1κP:2κ²N,N’-MCl₂] (M=Zn ( 3 ), Co ( 4 ), Ni ( 5 ), dmoPTA=3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) have been synthesized and characterized by elemental analysis and spectroscopic techniques. The crystal structures of 1 , 3 and 5 were obtained by single-crystal X-ray diffraction. The antiproliferative activity of the complexes was evaluated against colon cancer cell line Caco-2/TC7 by using the MTT protocol. The monometallic ruthenium complexes 1 and 2 were found to be inactive, but the bimetallic complexes 3 , 4 and 5 display an increased activity (IC₅₀ 3 : 9.07±0.27, 4 : 5.40±0.19, 5 : 7.15±0.30 μM) compared to cisplatin (IC₅₀=45.6±8.08 μM). Importantly, no reduction in normal cell viability was observed in the presence of the complexes. Experiments targeted to obtain information on the possible action mechanism of the complexes, such as cell cycle, ROS and gene expression studies, were performed. The results showed that the complexes display different properties and action mechanism depending on the nature of metal, M, bonded to the CH₃N_dmoPTA atoms.     

Microfluidic Production of Pyrophosphate Catalyzed by Mineral Membranes with Steep pH Gradients

Pyrophosphate might have functioned as an energy storage/currency molecule on early Earth, essential for the emergence of life. Here we synthesized mineral membranes involving iron(II), iron(III), and other divalent metal cations (calcium, manganese, cobalt, copper, zinc, and nickel) and tested their ability to catalyze the formation of pyrophosphate from phosphate and acetyl phosphate across steep pH gradients in microfluidic devices. We studied the chemical compositions of the precipitate membranes (which included vivianite, goethite, and green rust) using in situ and ex situ micro-Raman spectroscopy. The yields of pyrophosphate were determined by aqueous ³¹P NMR spectroscopy. We found that Fe²⁺ and Ca²⁺ were the best catalysts for pyrophosphate synthesis among investigated ions; Fe³⁺ and mixed-valence iron membranes were also able to promote pyrophosphate formation. In addition, the pH gradients across the membranes affected the pyrophosphate yields and the smallest pH gradient resulted in the highest yield. These results suggest a possible route of substrate phosphorylation in prebiotic hydrothermal systems.     

A tandem Petasis-Ugi multi component condensation reaction: solution phase synthesis of six dimensional libraries

Amino acids with three points of diversity generated from the Petasis boronic acid-Mannich reaction can be used as one of the four components of the Ugi condensation to prepare six dimensional libraries of dipeptide amides.     

Non-coalitional Core-Walras Equivalence in Finitely Additive Economies with Extremely Desirable Commodities

We prove an individualistic Core-Walras equivalence for finitely additive economies with a reflexive and separable commodity space, and with proper preferences.