Photocytotoxic organometallic compounds

Organometallic compounds have recently found applications in medicinal chemistry and as diagnostic tools in chemical biology. Naturally occurring biomolecules, viz., cobalamine, NiFe hydrogenase, Acetyl-CoA synthase, etc., also contain metal-carbon bonds. Among organometallic compounds having medicinal importance, (arene)ruthenium complexes, radioactive technetium complexes and ferrocene conjugates are notable ones. Applications of photoactive organometallic complexes or metal complexes conjugated with an organometallic moiety are of recent origin. Photodynamic therapy (PDT) is a promising method to treat cancer cells in presence of light. This review primarily focuses on different aspects of the chemistry of organometallic complexes showing photocytotoxic activities. Half-sandwich tungsten, iron or ruthenium complexes are known to show photonuclease and/or photo-crosslinking activity. Photoinduced organometallic CO releasing molecules also exert photocytotoxic activity. Attempts have been made in this review to highlight the photocytotoxic behavior of various metal complexes when conjugated with a photoactive organometallic moiety, viz., ferrocene.

Antimicrobial Properties of Nanostructured TiO2 Plus Fe Additive Thin Films Synthesized by a Cost-Effective Sol-Gel Process

We prepared thin films composed of pure TiO2 or TiO2 with an Fe additive (at concentrations of 0.2-0.8 wt%) via a simple and cost effective sol gel process, and tested their antifungal properties (against Candida albicans (MTCC-1637), Candida tropicalis (MTCC-184), Candida parapsilosis (MTCC-2509), and Candida glabrata (MTCC-3019) and antibacterial properties (against Staphylococcus faecalis (NCIM-2604) Staphylococcus epidermidis (NCIM-2493), Staphylococcus aureus (NCIL-2122), and Bacillus subtilis (NCIM-2549)). The films were deposited on glass and Si substrates and subjected to annealing at 400 degrees C for 3 h in ambient air. The film structural and morphological properties were investigated by X-ray photoelectron spectroscopy profilometry and scanning electron microscopy, respectively. Antifungal and antibacterial tests were conducted using the drop test method. Among the species examined, Candida albicans (MTCC-1637), and Staphylococcus aureus (NCIL-2122) showed complete colony formation inhibition after exposure for 4 h for the TiO2 loaded with 0.8 wt% Fe thin films. These results indicate that increasing the Fe concentration increased the antimicrobial activity, with complete inhibition of colony formation after 4 h exposure.

Estimation of vapour pressure and partial pressure of subliming compounds by low-pressure thermogravimetry

A method for the estimation of vapour pressure and partial pressure of subliming compounds under reduced pressure, using rising temperature thermogravimetry, is described in this paper. The method is based on our recently developed procedure to estimate the vapour pressure from ambient pressure thermogravimetric data using Langmuir equation. Using benzoic acid as the calibration standard, vapour pressure temperature curves are calculated at 80, 160 and 1000 mbar for salicylic acid and vanadyl bis-2,4-pentanedionate, a precursor used for chemical vapour deposition of vanadium oxides. Using a modification of the Langmuir equation, the partial pressure of these materials at different total pressures is also determined as a function of temperature. Such data can be useful for the deposition of multi-metal oxide thin films or doped thin films by chemical vapour deposition (CVD).

Ag@AgI, Core@Shell Structure in Agarose Matrix as Hybrid: Synthesis, Characterization, and Antimicrobial Activity

A novel in situ core@shell structure consisting of nanoparticles of Ag (Ag Nps) and AgI in agarose matrix (Ag@ AgI/agarose) has been synthesized as a hybrid, in order to have an efficient antibacterial agent for repetitive usage with no toxicity. The synthesized core@shell structure is very well characterized by XRD, UV-visible, photoluminescence, and TEM. A detailed antibacterial studies including repetitive cycles are carried out on Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) bacteria in saline water, both in dark and on exposure to visible light. The hybrid could be recycled for the antibacterial activity and is nontoxic toward human cervical cancer cells (HeLa cells). The water insoluble Ag@AgI in agarose matrix forms a good coating on quartz, having good mechanical strength. EPR and TEM studies are carried out on the Ag@AgI/agarose and the bacteria, respectively, to elucidate a possible mechanism for killing of the bacteria.

Reduction of aromatic nitro compounds to amines using zinc and aqueous chelating ethers: Mild and efficient method for zinc activation

A mild, environmentally friendly method for reduction of aromatic nitro group to amine is reported, using zinc powder in aqueous solutions of chelating ethers. The donor ether acts as a ligand and also serves as a co-solvent. Water is the proton source. This procedure is also a new method for the activation of zinc for electron transfer reduction of aromatic nitro compounds. The reduction is accomplished in a neutral medium and other reducing groups remained unaffected. The ethers used are dioxolane, 1,4-dioxane, ethoxymethoxyethane, dimethoxymethane, 1,2-dimethoxyethane, and diglyme.

Synthesis of benzofuran based 1,3,5-substituted pyrazole derivatives: As a new class of potent antioxidants and antimicrobials-A novel accost to amend biocompatibility

In search for a new antioxidant and antimicrobial agent with improved potency, we synthesized a series of benzofuran based 1,3,5-substituted pyrazole analogues (5a-l) in five step reaction. Initially, o-alkyl derivative of salicyaldehyde readily furnish corresponding 2-acetyl benzofuran 2 in good yield, on treatment with 1,8-diaza bicyclo5.4.0]undec-7-ene (DBU) in the presence of molecular sieves. Further, aldol condensation with vanillin, Claisen-Schmidt condensation reaction with hydrazine hydrate followed by coupling of substituted anilines afforded target compounds. The structures of newly synthesized compounds were confirmed by IR, H-1 NMR, C-13 NMR, mass, elemental analysis and further screened for their antioxidant and antimicrobial activities. Among the tested compounds 5d and 5f exhibited good antioxidant property with 50% inhibitory concentration higher than that of reference while compounds 5h and 5l exhibited good antimicrobial activity at concentration 1.0 and 0.5 mg/mL compared with standard, streptomycin and fluconazole respectively. (C) 2012 Elsevier Ltd. All rights reserved.

Oxidative DNA cleavage, cytotoxicity and antimicrobial studies of L-ornithine copper (II) complexes

New ternary copper (II) complexes, Cu(L-orn)(B)(Cl)](Cl center dot 2H(2)O) (1-2) where L-orn is L-ornithine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1) and 1,10-phenanthroline (phen, 2), were synthesized and characterized by various spectroscopic techniques. Complex 2 is characterized by the X-ray single crystallographic method. The complex shows a distorted square-pyramidal (4 + 1) CuN3OCl coordination sphere. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. Complex 2 shows appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA). The complexes were subjected to in vitro cytotoxicity studies against carcinomic human alveolar basal epithelial cells (A-549) and human epithelial (HEp-2) cells. The IC50 values of 1 and 2 are less than that of cisplatin against HEp-2 cell lines. MIC values for 1 against the bacterial strains Streptococcus mutans and Pseudomonas aeruginosa are 0.5 mM. (C) 2012 Elsevier Ltd. All rights reserved.

Curcumin reduces the antimicrobial activity of ciprofloxacin against Salmonella Typhimurium and Salmonella Typhi

Typhoidal and non-typhoidal infection by Salmonella is a serious threat to human health. Ciprofloxacin is the last drug of choice to clear the infection. Ciprofloxacin, a gyrase inhibitor, kills bacteria by inducing chromosome fragmentation, SOS response and reactive oxygen species (ROS) in the bacterial cell. Curcumin, an active ingredient from turmeric, is a major dietary molecule among Asians and possesses medicinal properties. Our research aimed at investigating whether curcumin modulates the action of ciprofloxacin. We investigated the role of curcumin in interfering with the antibacterial action of ciprofloxacin in vitro and in vivo. RTPCR, DNA fragmentation and confocal microscopy were used to investigate the modulation of ciprofloxacin-induced SOS response, DNA damage and subsequent filamentation by curcumin. Chemiluminescence and nitroblue tetrazolium reduction assays were performed to assess the interference of curcumin with ciprofloxacin-induced ROS. DNA binding and cleavage assays were done to understand the rescue of ciprofloxacin-mediated gyrase inhibition by curcumin. Curcumin interferes with the action of ciprofloxacin thereby increasing the proliferation of Salmonella Typhi and Salmonella Typhimurium in macrophages. In a murine model of typhoid fever, mice fed with curcumin had an increased bacterial burden in the reticuloendothelial system and succumbed to death faster. This was brought about by the inhibition of ciprofloxacin-mediated downstream signalling by curcumin. The antioxidant property of curcumin is crucial in protecting Salmonella against the oxidative burst induced by ciprofloxacin or interferon (IFN), a pro-inflammatory cytokine. However, curcumin is unable to rescue ciprofloxacin-induced gyrase inhibition. Curcumins ability to hinder the bactericidal action of ciprofloxacin and IFN might significantly augment Salmonella pathogenesis.

Photophysical behavior of poly(propyl ether imine) dendrimer in the presence of nitroaromatic compounds

This paper deals with a study of the photophysical property of poly(ether imine) (PETIM) dendritic macromolecule in the presence of aromatic compounds. The inherent photoluminescence property of the dendrimer undergoes quenching in the presence of guest aromatic nitro-compounds. From life-time measurements study, it is inferred that the lifetimes of luminescent species of the dendrimer are not affected with nitrophenols as guest molecules, whereas nitrobenzenes show a marginal change in the lifetimes of the species. Raman spectral characteristic of the macromolecular host-guest complex is conducted in order to identify conformational change of the dendrimer and a significant change in the stretching frequencies of methylene moieties of the dendrimer is observed for the complex with 1,3,5-trinitrobenzene, when compared to other complexes, free host and guest molecules. The photophysical behavior of electron-rich, aliphatic, neutral dendritic macromolecule in the presence of electron-deficient aromatic molecules is illustrated in the present study. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis, antimicrobial, DNA-binding and photonuclease studies of Cobalt(III) and Nickel(II) Schiff base complexes

New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.

Interaction of Silver Nanoparticles with Serum Proteins Affects Their Antimicrobial Activity In Vivo

The emergence of multidrug-resistant bacteria is a global threat for human society. There exist recorded data that silver was used as an antimicrobial agent by the ancient Greeks and Romans during the 8th century. Silver nanoparticles (AgNPs) are of potential interest because of their effective antibacterial and antiviral activities, with minimal cytotoxic effects on the cells. However, very few reports have shown the usage of AgNPs for antibacterial therapy in vivo. In this study, we deciphered the importance of the chosen methods for synthesis and capping of AgNPs for their improved activity in vivo. The interaction of AgNPs with serum albumin has a significant effect on their antibacterial activity. It was observed that uncapped AgNPs exhibited no antibacterial activity in the presence of serum proteins, due to the interaction with bovine serum albumin (BSA), which was confirmed by UV-Vis spectroscopy. However, capped AgNPs with citrate or poly(vinylpyrrolidone)] exhibited antibacterial properties due to minimized interactions with serum proteins. The damage in the bacterial membrane was assessed by flow cytometry, which also showed that only capped AgNPs exhibited antibacterial properties, even in the presence of BSA. In order to understand the in vivo relevance of the antibacterial activities of different AgNPs, a murine salmonellosis model was used. It was conclusively proved that AgNPs capped with citrate or PVP exhibited significant antibacterial activities in vivo against Salmonella infection compared to uncapped AgNPs. These results clearly demonstrate the importance of capping agents and the synthesis method for AgNPs in their use as antimicrobial agents for therapeutic purposes.

Information content of molecular graph and prediction of gas phase thermal entropy of organic compounds

Entropy is a fundamental thermodynamic property that has attracted a wide attention across domains, including chemistry. Inference of entropy of chemical compounds using various approaches has been a widely studied topic. However, many aspects of entropy in chemical compounds remain unexplained. In the present work, we propose two new information-theoretical molecular descriptors for the prediction of gas phase thermal entropy of organic compounds. The descriptors reflect the bulk and size of the compounds as well as the gross topological symmetry in their structures, all of which are believed to determine entropy. A high correlation () between the entropy values and our information-theoretical indices have been found and the predicted entropy values, obtained from the corresponding statistically significant regression model, have been found to be within acceptable approximation. We provide additional mathematical result in the form of a theorem and proof that might further help in assessing changes in gas phase thermal entropy values with the changes in molecular structures. The proposed information-theoretical molecular descriptors, regression model and the mathematical result are expected to augment predictions of gas phase thermal entropy for a large number of chemical compounds.

In vitro and in silico biological studies of novel thiazolo3,2-a]pyrimidine-6-carboxylate derivatives

In the present study, we report the synthesis, characterization of new series of thiazolo3,2-a]pyrimidine-6-carboxylate derivatives 3a-f and 4a-f. The newly synthesized compounds were screened for in vitro antimicrobial and antiviral activities. The probable mode of action of these active compounds was determined through in silico docking study by docking the receptor methionyl-tRNA synthetase and human inosine-5'-monophosphate dehydrogenase (IMPDH) for antibacterial and antiviral activities, respectively. Among the compounds, 4c exhibited excellent in vitro antimicrobial activity against all tested strains with binding and docking energies -35.6 and -12.4 kcal/mol, respectively. The antiviral studies were carried out for the selected compounds in which 4a exhibited 73.69 and 54.42 % of inhibition of buffalopox and camelpox viruses, respectively. Furthermore, compound 4a showed minimum docking and binding energy along with the maximum hydrogen/hydrophobic interaction with IMPDH. The study contributes towards identification and screening of potential antimicrobial and antiviral agent's against the pathogens.

Synthesis, antimicrobial and cytotoxic activities of pyrimidinyl benzoxazole, benzothiazole and benzimidazole

A variety of pyrimidinyl benzoxazoles, benzothiazoles and benzimidazoles linked by thio, methylthio and amino moieties were prepared and studied their antimicrobial and cytotoxic activities. The compound pyrimidinyl bis methylthio benzimidazole 22 was a potent antimicrobial agent particularly against Staphylococcus aureus (29 mm, MIC 12.5 mu g/mL) and Penicillium chrysogenum (38 mm, MIC 12.5 mu g/mL). The amino linked pyrimidinyl bis benzothiazole 24 exhibited cytotoxic activity on A549 cells with IC50 value of 10.5 mu M. (C) 2014 Elsevier Masson SAS. All rights reserved.

Antimicrobial and conducting polymer substrate derived from hybrid structures of silver nanoparticles and multiwall carbon nanotubes

Hybrid nanocomposites of polycaprolactone (PCL) with multiwall carbon nanotubes (MWNTs) and silver nanoparticles (nAg) were prepared by melt mixing. Synergetic effect of the two nanofillers (MWNT and nAg) in PCL matrix was evaluated for dielectric and antibacterial properties. Dielectric results showed that the addition of nAg as filler in PCL matrix (PCL/nAg) had no effect on conductivity, whereas addition of MWNT in PCL matrix (PCL/MWNT) caused a sharp increase in conductivity of PCL. Interestingly, the hybrid nanocomposite (PCL/MWNT/nAg) incorporating MWNT and nAg also exhibited high electrical conductivity. The hybrid composite was found to have antibacterial property similar to that of PCL/nAg composite for lower loading of nAg. This study demonstrates that the synergetic interaction of the nanofillers in the hybrid nanocomposite improves both electrical conductivity and antibacterial properties of PCL.