Allyl palladium complexes bearing carbohydrate-based N-heterocyclic carbenes: Anticancer agents for selective and potent in vitro cytotoxicity

Novel allyl palladium compounds stabilized by carbohydrate-based N-heterocyclic carbenes (NHCs) were prepared and characterized by nuclear magnetic resonance, high-resolution mass spectrometry and elemental analysis. The antiproliferative activity of the compounds was tested on a panel of different tumor lines, especially ovarian cancer and MRC-5 human lung fibroblasts (nontumor cells). These experiments showed that both mixed NHC/PPh₃ and NHC/PTA (PTA = 1,3,5-triaza-7-phosphaadamantane) allyl complexes have IC₅₀ (half maximal inhibitory concentration) values comparable and sometimes even significantly lower than cisplatin. Moreover, the mixed NHC/PTA allyl complexes exhibit good activity toward the seven tumor lines tested with a substantial inactivity against normal cells, a necessary condition to avoid the general cytotoxicity of a metallo-drug. Furthermore, this subclass of compounds proved particularly active on the A549 lung cancer tumor line (up to 100-fold more cytotoxic than cisplatin) and exhibited satisfactory cytotoxicity against KURAMOCHI and OVCAR3 cell lines, which are currently considered the best in vitro models for serous ovarian cancer, the most lethal tumor for women worldwide.     

Rhodium and iridium complexes containing the anion of 1-phenyl-3-methyl-4-benzoyl- pyrazolone-5, a sophisticated analogue of β-diketones

Several (diolefin)M(A) complexes (M = Rh, Ir) were prepared, where AH is 1-phenyl-3-methyl- 4-benzoylpyrazolone-5, a very stable asymmetric analogue of acetylacetone. In these complexes the diolefin could be replaced by one mole of (Ph₂PCH₂CH₂)₂, two of CO or of PPh₃, or three of CNBu^t, while 1,10-phenanthroline displaced the chelating ligand to yield [(cyclooctadiene)Rh(phen)]⁺ (A)^?. Some compounds X?Y (X?Y = iodine or MeI) added oxidatively yielding the corresponding trivalent species. Using ³¹P NMR spectra the presence of the expected steric isomers was detected in (Ph₃P)(CO)Rh(A) and in (Ph₃P) (CO)Rh(A)(X)(Y).     

Some correspondence between classes of incidence structures with tolerance

Summary We consider structures (G,T,J) whereT is a tolerance (i.e. a reflexive and symmetric binary relation) on the setG (whose elements are called lines) andJ is 0271 0247 V 3 a family of sets of mutuallyT-related lines, called incidence structures with tolerance (briefly: ISTs). We study certain operators between the tolerances on a setG and certain classes of ISTs defined onG.

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Riassunto Una struttura d'incidenza con tolleranza (brevemente IST) è una terna (G,T,J) doveT è una tolleranza (cioè una relazione binaria che sia riflessiva e simmetrica) su un insieme non vuotoG (i cui elementi sono detti rette) eJ è una famiglia di insiemi 0271 0247 V 3 di rette in mutua relazioneT. In questa nota noi studiamo certi operatori tra le tolleranze su un insiemeJ e 0271 0247 V 2 certe classi di ISTs definite suG.

     

Studies on immobilizd lipase in hydrophobic sol-gel

The hydrolysis of tetraethoxysilane using the sol-gel process was used to produce silica matrices, and these were tested for the immobilization of lipase from Candida rugosa by three methods: physical adsorption, covalent binding, and gel entrapment in the presence and absence of polyethylene glycol (PEG-1450). The silica matrices and their derivatives were characterized regarding particle size distribution, specific surface area, pore size distribution (Brunauer, Emmett, and Teller [B.E.T.] method), yield of grafting (thermogravimetric analyzer [TGA]), and chemical composition (Fourier transform infrared). Immobilization yields based on recovered lipase activity varied from 3.0 to 32.0%, and the highest efficiency was attained when lipase was encapsulated in the presence of PEG.     

Fuel‐Selective Transient Activation of Nanosystems for Signal Generation

The transient activation of function using chemical fuels is common in nature, but much less in synthetic systems. Progress towards the development of systems with a complexity similar to that of natural ones requires chemical fuel selectivity. Here, we show that a self‐assembled nanosystem, composed of monolayer‐protected gold nanoparticles and a fluorogenic peptide, is activated for transient signal generation only in case the chemical fuel matches the recognition site present at the nanoparticle surface. A modification of the recognition site in the nanosystem completely changes the chemical fuel selectivity. When two nanosystems are simultaneously present, the selectivity expressed by the system depends on the concentration of nucleotide added.     

Hybrid Inorganic-Organic Sol–Gel Coatings in the SiO2-TiO2 System

In the present work, the influence of substituted Si-alkoxides on the structural and optical properties of films obtained in the SiO₂-TiO₂ system was studied. Methyltriethoxysilane (MTEOS) and 3-(tri-methoxysilyl)propyl methacrylate (TSPM) were used as SiO₂ sources and Ti(OBu)₄ was used as TiO₂ source. Acetylacetone was added to the Ti(OBu)₄ as chelating agent and the synthesis was carried out in acid medium. The films were deposited on oxidized Si-wafers by spin-coating. The films were characterized by XRD, spectro-ellipsometry (SE), and atomic force microscopy (AFM). The results obtained have shown that in the case of hybrid films the desired thickness could be obtained in a single deposition step. The thickness of the films and the optical properties are controlled by the bulkiness of the organic substitute bounded to Si. Among other optical applications, the potential use of such films as optical waveguides is proposed.     

Nuclear analyses of the Pietroasa gold hoard

By means of nuclear analyses the concentrations of Au, Ag, Cu, Ir, Os, Pt, Co and Hg were measured in the 12 artifacts of the gold hoard discovered in 1837 at Pietroasa, Buzäu county in Romania. The concentrations of the first four elements were used to compare different stylistic groups assumed by historians. Comparisons with gold nuggets from the old Dacian territory and gold Roman imperial coins were also made. A good agreement was found with the oldest hypothesis which considers that the hoard is represented by three styles appropriated mainly by the Goths.     

Understanding and controlling the efficiency of Au24M(SR)18 nanoclusters as singlet-oxygen photosensitizers

Singlet oxygen, ¹O₂, can be generated by molecules that upon photoexcitation enable the ³O₂ → ¹O₂ transition. We used a series of atomically precise Au₂₄M(SR)₁₈ clusters, with different R groups and doping metal atoms M. Upon nanosecond photoexcitation of the cluster, ¹O₂ was efficiently generated. Detection was carried out by time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The resulting TREPR transient yielded the ¹O₂ lifetime as a function of the nature of the cluster. We found that: these clusters indeed generate ¹O₂ by forming a triplet state; a more positive oxidation potential of the molecular cluster corresponds to a longer ¹O₂ lifetime; proper design of the cluster yields results analogous to those of a well-known reference photosensitizer, although more effectively. Comprehensive kinetic analysis provided important insights into the mechanism and driving-force dependence of the quenching of ¹O₂ by gold nanoclusters. Understanding on a molecular basis why these molecules may perform so well in ¹O₂ photosensitization is instrumental to controlling their performance.

Atomically precise Au₂₄M(SR)₁₈ clusters were used as singlet-oxygen photosensitizers. Comprehensive kinetic analysis provided insights into the mechanism and driving-force dependence of the quenching of ¹O₂ by gold nanoclusters.     

Grafting of cyclodextrins onto filter paper

Grafting of cyclodextrins and cyclodextrins derivatives on cellulosic surface, such as paper or filter paper, provides hosting cavities that can include a large variety of chemicals for specific cellulose finishing. In this study grafting of monocholorotriazinyl-β-cyclodextrin (MCT-β-CD) and β-cyclodextrin (β-CD) to filter paper has been performed. β-cyclodextrin has been bonded to filter paper using 1,4-butanediol diglycidyl ether as the crosslinking agent. The untreated and treated filter papers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), demonstrating the covalent binding of cyclodextrins to filter paper. The quantification of β-CD and MCT-β-CD grafted to filter paper was determined by the dye extinction method with the inclusion of phenolphthalein. The final β-CD content amounted to 15.9 μmol per gram of support (1.8% by weight), and 72.8 μmol per gram of support (11.3% by weight) for MCT-β-CD.     

Synthesis of 13c-labelled [s]-proline and its conformational analysis by nuclear magnetic resonance

In order to analyze completely the ring conformation of [S]-Proline (l-thiazolidine-4-carboxylic acid) this compound has been synthesized with its C_δ atom enriched at 90% in ¹³C. The ¹H-¹H, ¹³C-¹H, ¹³C-¹³C vicinal coupling constants measured at several pH values describe well the geometry of the thiazolidine ring. The results suggest that the ring has an average planar conformation only in a narrow range of pH close to the pK of the amine group. Above and below this pH the ring tends to adopt preferentially the S_γendo and S_γexo puckered conformations respectively. It is concluded that a good correlation exists between the value of the dihedral angle ø and the character S_γendo or S_γexo of the ring.