New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

Mechanism and linear free energy relationships in the kinetics of formation of bicyclo[3.3.1]nonane derivatives from 1,3,5‐trinitrobenzene,phenyl‐substituted 1‐benzyl‐1‐(ethoxycarbonyl)‐2‐propanones,and triethylamine

The kinetics and mechanism of cyclization of the anionic sigma complex obtained from the reaction of 1,3,5‐trinitrobenzene (TNB) and 1‐benzyl‐1‐(ethoxycarbonyl)‐2‐propanone (BEP) in the presence of triethylamine (NEt₃) have been studied in CH₃CN–CH₃OH (50% v/v). The order of the reaction has been found to be zero in TNB and BEP, unity in NEt₃, and negative and nonintegral in triethylammonium chloride. The rate has been observed to increase slightly with an increase in the concentration of the added salt (tetraethylammonium chloride). The rate constants for the formation of bicyclic adducts from phenyl‐substituted BEP and TNB in the presence of triethylamine have been correlated with σ values. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 467–473, 2011     

In vitro evaluation of antiproliferative effect of ethyl gallate against human oral squamous carcinoma cell line KB

Although some polyphenols are known to possess anticancer activity against different cancer cell lines through induction of apoptosis, the mode of antiproliferative effect of ethyl gallate against human oral squamous carcinoma cell line KB was not studied until now. Therefore, the antiproliferative effect of ethyl gallate was evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay in comparison with the reference drug paclitaxel. Generation of reactive oxygen species, mitochondrial membrane potential loss, DNA damage and apoptosis were determined using 2,7-diacetyldichlorofluorescein fluorescence, uptake of rhodamine-123 by mitochondria, comet assay and acridine orange/ethidium bromide dual-dye staining method. Both ethyl gallate and paclitaxel exhibited cytotoxicity in a dose-dependent manner. The 50% inhibitory concentration for ethyl gallate was 30 and 20 μg/mL for paclitaxel. A volume of 50 μg/mL of ethyl gallate was found to be significantly effective (P < 0.05) in controlling the cancer cell proliferation leading to acute apoptosis.     

Spectroscopic investigation of heterogeneous Ziegler-Natta catalysts: Ti and Mg chloride tetrahydrofuranates, their interaction compound, and the role of the activator

X-ray powder diffraction (XRPD), Infrared, Raman, and UV/Vis spectroscopy have been used to investigate the structural, vibrational, and optical properties of Ti and Mg chloride tetrahydrofuranates as precursors of heterogeneous Ziegler-Natta catalysts for polyethylene production; as well as their interaction compound (pro-catalyst) and the final catalyst obtained after interaction with the AlR(3) activator. Although the structure of the precursors and of the pro-catalyst were well known, that of the catalyst (obtained by reaction of the pro-catalyst with AlR(3)) was not easily obtainable from XRPD data. IR and Raman spectroscopy provided important information on tetrahydrofuran (thf) coordination and on the ν(M-Cl) region; whereas UV/Vis spectroscopy gave the direct proof on both the formal oxidation state and the coordination environment of the active Ti sites. Those presented herein are among the first direct experimental data on the structure of the active Ti sites in Ziegler-Natta catalysts, and can be used to validate the many computational studies that have been increasing exponentially in the last few decades.     

Water-dispersible sugar-coated iron oxide nanoparticles. An evaluation of their relaxometric and magnetic hyperthermia properties

Synthesis of functionalized magnetic nanoparticles (NPs) for biomedical applications represents a current challenge. In this paper we present the synthesis and characterization of water-dispersible sugar-coated iron oxide NPs specifically designed as magnetic fluid hyperthermia heat mediators and negative contrast agents for magnetic resonance imaging. In particular, the influence of the inorganic core size was investigated. To this end, iron oxide NPs with average size in the range of 4-35 nm were prepared by thermal decomposition of molecular precursors and then coated with organic ligands bearing a phosphonate group on one side and rhamnose, mannose, or ribose moieties on the other side. In this way a strong anchorage of the organic ligand on the inorganic surface was simply realized by ligand exchange, due to covalent bonding between the Fe(3+) atom and the phosphonate group. These synthesized nanoobjects can be fully dispersed in water forming colloids that are stable over very long periods. Mannose, ribose, and rhamnose were chosen to test the versatility of the method and also because these carbohydrates, in particular rhamnose, which is a substrate of skin lectin, confer targeting properties to the nanosystems. The magnetic, hyperthermal, and relaxometric properties of all the synthesized samples were investigated. Iron oxide NPs of ca. 16-18 nm were found to represent an efficient bifunctional targeting system for theranostic applications, as they have very good transverse relaxivity (three times larger than the best currently available commercial products) and large heat release upon application of radio frequency (RF) electromagnetic radiation with amplitude and frequency close to the human tolerance limit. The results have been rationalized on the basis of the magnetic properties of the investigated samples.     

Effect of ionic liquid on dielectric, mechanical and dynamic mechanical properties of multi-walled carbon nanotubes/polychloroprene rubber composites

This paper focuses on the influence of ionic liquid on carbon nanotube based elastomeric composites. Multi-walled carbon nanotubes (MWCNTs) are modified using an ionic liquid at room temperature, 1-butyl 3-methyl imidazolium bis (trifluoromethylsulphonyl) imide (BMI) and modified MWCNTs exhibit physical (cation–π/π–π) interaction with BMI. The polychloroprene rubber (CR) composites are prepared using unmodified and BMI modified MWCNTs. The presence of BMI not only increases the alternating current (AC) electrical conductivity and polarisability of the composites but also improves the state of dispersion of the tubes as observed from dielectric spectroscopy and transmission electron microscopy respectively. In addition to the hydrodynamic reinforcement, the formation of improved filler–filler networks is reflected in the dynamic storage modulus (E′) for modified MWCNTs/CR composites in amplitude sweep measurement upon increasing the proportion of BMI. Hardness and mechanical properties are also studied for the composites as a function of BMI.     

2-Methylpyridinium/pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olates as potent anticonvulsant agents—synthesis and crystal structure

The molecular salt, 2-methylpyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropy-rimidin-4-olate) (I), is prepared from the ethanolic solution of 1-chloro-2,4-dinitrobenzene, pyrimidine-2,4,6-(1H,3H,5H)-trione (barbituric acid) and 2-methylpyridine at room temperature, and the molecular salt, pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate (II), is prepared from the same reactants, by dissolving them in hot DMSO and ethanol mixture at 70°C. The structures of I and II are characterized by visible, IR, ¹H-NMR, ¹³C-NMR and elemental analysis and confirmed by single crystal X-ray analysis. Both the salts crystallize in triclinic crystal system with sp. gr. $P\bar 1$ . They possess noticeable anticonvulsant activity even at low concentration (25 mg/kg). Acute toxicity studies of these complexes indicate that LD₅₀ values are greater than 1500 mg/kg and the tested animals do not show any behavioural changes.     

Studies on Squalene Biosynthesis and the Standardization of Its Extraction Methodology from Saccharomyces cerevisiae

Applied Biochemistry and Biotechnology - In this study, a homogenization-based extraction method was developed and was compared to five conventional methods of squalene extraction. Squalene...     

Visible-Light-Driven One-Pot Synthesis of Benzimidazoles,Benzothiazoles, and Quinazolinones Catalyzed by Scalable and Reusable Ba-Doped CoMoO4 Nanoparticles Under Air Atmosphere

Herein we report a simple and efficient oxidative coupling of various aryl methyl amines with diverse coupling partners, such as o-phenylenediamine (benzene-1,2-diamine), 2-aminobenzenethiol and 2-aminobenzamide, to synthesize the corresponding heterocycles using scalable and reusable heterogeneous catalysts under visible light irradiation. A systematic investigation led to the synthesis of benzimidazoles, benzothiazoles and quinazolinones under air atmosphere in very good to excellent yields. The strategy is atom economical and found to be tolerance towards different functional groups, and wide range of substrate scope. Furthermore, the methodology was demonstrated for its suitability on scale up and reusability. The density functional theory (DFT) calculations and the analysis of band structures of pristine and Ba doped CoMoO₄ systems showed that the doping of Ba in place of Co improved the catalytic performance of the system.     

New fluorescent probes for carbonic anhydrases

We report the synthesis and fluorescence properties of naphthalenesulfonamide derivatives as active site probes for carbonic anhydrases.