New Nanostructured Materials Based on Mesoporous Silica Loaded with Ru(II)/Ru(III) Complexes with Anticancer and Antimicrobial Properties.

A new series of nanostructured materials was obtained by functionalization of SBA-15 mesoporous silica with Ru(II) and Ru(III) complexes bearing Schiff base ligands derived from salicylaldehyde and various amines (1,2-diaminocyclohexane, 1,2-phenylenediamine, ethylenediamine, 1,3-diamino-2-propanol, N,N-dimethylethylenediamine, 2-aminomethyl-pyridine, and 2-(2-aminoethyl)-pyridine). The incorporation of ruthenium complexes into the porous structure of SBA-15 and the structural, morphological, and textural features of the resulting nanostructured materials were investigated by FTIR, XPS, TG/DTA, zeta potential, SEM, and N2 physisorption. The ruthenium complex-loaded SBA-15 silica samples were tested against A549 lung tumor cells and MRC-5 normal lung fibroblasts. A dose-dependent effect was observed, with the highest antitumoral efficiency being recorded for the material containing [Ru(Salen)(PPh3)Cl] (50%/90% decrease in the A549 cells' viability at a concentration of 70 µg/mL/200 µg/mL after 24 h incubation). The other hybrid materials have also shown good cytotoxicity against cancer cells, depending on the ligand included in the ruthenium complex. The antibacterial assay revealed an inhibitory effect for all samples, the most active being those containing [Ru(Salen)(PPh3)Cl], [Ru(Saldiam)(PPh3)Cl], and [Ru(Salaepy)(PPh3)Cl], especially against Staphylococcus aureus and Enterococcus faecalis Gram-positive strains. In conclusion, these nanostructured hybrid materials could represent valuable tools for the development of multi-pharmacologically active compounds with antiproliferative, antibacterial, and antibiofilm activity.

Homo- and heterometallic complexes of Zn(II), {Zn(II)Au(I)}, and {Zn(II)Ag(I)} with pentadentate Schiff base ligands as promising anticancer agents.

Two families of homo- and heterometallic complexes, [Zn2L1(µ-OH)(H2O)2](ClO4)2, [Zn2L2(µ-OH)(H2O)2](ClO4)2, [Zn2L3(µ-OH)(H2O)2](ClO4)2, 1∞[{L1Zn2(µ-OH)}{µ-[Ag(CN)2]}](ClO4), [{L1Zn2(µ-OH)}2{µ-[Au(CN)2]}{[Au(CN)2]2}](ClO4)·H2O, 1∞[{L2Zn2(µ3-OH)}2(H2O){µ-[Ag(CN)2]}](ClO4)3·THF·0.5MeOH, 1∞[{L2Zn2(µ3-OH)}2(H2O){µ-[Au(CN)2]}](ClO4)3·THF·H2O, and 1∞[{L3Zn2(µ-OH)}{µ-[Ag(CN)2]}][Ag(CN)2]·H2O, respectively, have been synthesized and characterized. The Schiff bases used as ligands were obtained by condensation reactions of 2,6-diformyl-p-cresol with N,N-dimethyl-ethylenediamine (HL1), 2-aminomethyl-pyridine (HL2), and 2-aminoethyl-pyridine (HL3), respectively. The cytotoxic/cytostatic and genotoxic effects in cultured human MCF-7 (luminal type A breast cancer), MDA-MB-231 (triple negative breast cancer), HeLa (cervical carcinoma), and Lep-3 (non-tumor embryonal fibroblastoid cells) were studied. The investigations were performed by thiazolyl blue tetrazolium bromide test (MTT test), neutral red uptake cytotoxicity assay, crystal violet staining, hematoxylin and eosin staining, double staining with acridine orange and propidium iodide, AnnexinV/FITC, and Comet assay in short-term experiments (24-72 h, with monolayer cell cultures) as well as by 3D colony-forming method in long-term experiments (28 days, with 3D cancer cell colonies). The results obtained revealed that: (i) applied at a concentration range of 0.1-100 µg mL-1, the compounds investigated decrease in a time- and concentration-dependent manner the viability and/or proliferation of the treated cells; (ii) complexes of {Zn(II)Au(I)} show relatively higher cytotoxic/genotoxic activity and antitumor potential as compared to {Zn(II)Ag(I)}; (iii) some of the complexes demonstrate more pronounced cytotoxic potential than commercially available antitumor agents cisplatin, oxaliplatin, and epirubicin.

Novel Magnetic Nanocomposites Based on Carboxyl-Functionalized SBA-15 Silica for Effective Dye Adsorption from Aqueous Solutions.

In this study, three novel magnetic nanocomposites based on carboxyl-functionalized SBA-15 silica and magnetite nanoparticles were prepared through an effective and simple procedure and applied for methylene blue (MB) and malachite green G (MG) adsorption from single and binary solutions. Structure, composition, morphology, magnetic, and textural properties of the composites were thoroughly investigated. The influence of the amount of carboxyl functional groups on the physicochemical and adsorptive properties of the final materials was investigated. The capacity of the synthesized composites to adsorb MB and MG from single and binary solutions and the factors affecting the adsorption process, such as contact time, solution pH, and dye concentration, were assessed. Kinetic modelling showed that the dye adsorption mechanism followed the pseudo-second-order kinetic model, indicating that adsorption was a chemically controlled multilayer process. The adsorption rate was simultaneously controlled by external film diffusion and intraparticle diffusion. It was evidenced that the molecular geometry of the dye molecule plays a major role in the adsorption process, with the planar geometry of the MB molecule favoring adsorption. The analysis of equilibrium data revealed the best description of MB adsorption behavior by the Langmuir isotherm model, whereas the Freundlich model described better the MG adsorption.

Triphenylbismuth(v) di[(iso)nicotinates] - transmetallation agents or divergent organometalloligands? First organobismuth(v)-based silver(i) coordination polymers.

The reaction of Ph3BiCl2 with alkali salts of isonicotinic and nicotinic acids afforded Ph3Bi[O(O)CC5H4N-4]2 (1) and Ph3Bi[O(O)CC5H4N-3]2 (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal C3BiO2 core, with the phenyl groups in equatorial positions. The potential use of 1 and 2 as ditopic organometalloligands was investigated. The reaction of 1 or 2 with Me3SnCl (1 : 2 molar ratio) resulted in carboxylato ligand exchange and the formation of Me3Sn[O(O)CC5H4N-4] (3) and Me3Sn[O(O)CC5H4N-3] (4) besides Ph3BiCl2. The crystals of both 3 and 4 contain 1-D coordination polymers built through intermolecular N → Sn interactions. The treatment of Ni[S2P(OiPr)2]2 with 1 and 2, respectively, resulted, in addition to di(carboxylato)nickel(ii) derivatives, in isolation of Ph3Bi and the disulphane [(iPrO)2P(S)S]2. New coordination polymers were obtained by reacting 1 and 2 with various silver(i) salts: [Ag{Ph3Bi[O(O)CC5H4N-4]2}(OTf)] (5), [Ag{Ph3Bi[O(O)CC5H4N-3]2}(OTf)]·CH2Cl2 (6·CH2Cl2), [Ag{Ph3Bi[O(O)CC5H4N-4]2}](SbF6)·2THF (7·2THF), [Ag{Ph3Bi[O(O)CC5H4N-3]2}](SbF6)·CH2Cl2 (8·CH2Cl2) and [Ag{Ph3Bi[O(O)CC5H4N-3]2}(NO3)]·CH2Cl2 (9·CH2Cl2). The crystal structures of 5 and 6 can be described as 1-D chains linked by triflate bridges in pairs of chains and 2-D networks, respectively. Compound 7 features a 2-D grid-like topology of the network, with tecton 1 acting as a tridentate ligand through both nitrogen and one oxygen atoms. The linker 2 molecules adopt either cis (compound 6) or trans (compounds 8 and 9) conformation. Complexes 8 and 9 are 1-D chain polymers exhibiting zig-zag and wavy motifs, respectively. The dimensionality of the structures is extended by the presence of supramolecular interactions (ππ, AgAg, AgO).

Two different types of diabetes mellitus in pancreatic cancer population. Comparative study between new onset and long standing diabetes mellitus on 76 patients with pancreatic cancer.

BACKGROUND: There are some studies which have reported a higher diagnosis probability for PC if the DM occurred within the past 2-3 years. Information on the clinical profile of pancreatic cancer (PC) associated with diabetes mellitus (DM) is limited. The aim of the study was to compare clinic-morphological features in patients with new onset DM and PC and long lasting DM and PC, in order to detect new factors or markers which can help in early diagnosis of PC. METHODS: This study included 76 patients with pancreatic cancer admitted between 2000-2009 in the 4th Medical Clinic Cluj-Napoca; in group A 56 patients with PC and new onset of DM (< 24 months duration) were included and in group B 20 patients with PC and long standing diabetes (> 60 months duration) were included. We compared the demographic, clinical, biochemical and morphological characteristics of new onset or long lasting DM and pancreatic cancer. RESULTS: New onset DM was more prevalent (74% vs. 26%, p < .05) than long lasting DM among patients with PC. The patients with long lasting DM had a greater frequency of urban environment (100% vs. 55.6% p = .02), a higher body mass index (BMI)(32.1 SD 8.4 vs. 29.9 SD 6.7 kg/m2, p = .05), higher fasting blood glucose levels (182 mg/dL vs. 134 mg/dL, p = .008) and urinary ketone bodies (60% vs. 10.7%, p = .002) compared with those with new-onset DM and PC. There was no statistical difference regarding gender, median age, blood group, location and staging of tumours, long and hard alcohol and cigarettes consumption, between group A and B. CONCLUSIONS: New onset DM was more significantly frequent than long lasting DM in patients with PC. New onset diabetes DM associated with PC is frequent, mild and non-decompensated. In patients with PC and long lasting DM, the metabolic status and diabetes are imbalanced.