Calculations of vibrational frequencies, Raman activities and degrees of depolarization for complexes involving water, methanol and ethanol

Raman activities and degrees of depolarization are reported for 14 complexes involving methanol, ethanol and water using the MP2/aug-cc-pVDZ model. For ethanol both trans and gauche isomers are considered. The red-shifts of the OH stretching and the blue shifts of the bending tau(CO-OH) mode were analyzed for the proton-donor molecules upon hydrogen bond. The shift of the nu(CO) stretching mode of the alcohol molecules are also analyzed and found to be specific giving characterization of the amphoteric relation, being positive for the proton-acceptor and negative for the proton-donor molecule. (c) 2008 Elsevier B.V. All rights reserved.

Synthesis, characterization, X-ray structure and in vitro anti mycobacterial and antitumoral activities of Ru(II) phosphine/diimine complexes containing the ""SpymMe(2)"" ligand, SpymMe(2)=4,6-dimethyl-2-mercaptopyrimidine

The reaction of cis-[RuCl2(dppb)(N-N)], dppb = 1,4-bis(diphenylphosphino)butane, complexes with the ligand HSpymMe(2), 4,6-dimethyl-2-mercaptopyrimidine, yielded the cationic complexes [Ru(SpymMe(2))(dppb)(N-N)]PF6, N-N = bipy (1) and Me-bipy (2), bipy = 2,2`-bipyridine and Me-bipy = 4,4`dimethyl-2,2`-bipyridine, which were characterized by spectroscopic and electrochemical techniques and X-ray crystallography and elemental analysis. Additionally, preliminary in vitro tests for antimycobacterial activity against Mycobacterium tuberculosis H37Rv ATCC 27264 and antitumor activity against the MDA-MB-231 human breast tumor cell line were carried out on the new complexes and also on the precursors cis-[RuCl2(dppb)(N-N)], N-N = bipy (3) and Me-bipy (4) and the free ligands dppb, bipy, Me-bipy and SpymMe(2). The minimal inhibitory concentration (MIC) of compounds needed to kill 90% of mycobacterial cells and the IC50 values for the antitumor activity were determined. Compounds 1-4 exhibited good in vitro activity against M. tuberculosis, with MIC values ranging between 0.78 and 6.25 mu g/mL, compared to the free ligands (MIC of 25 to >50 mu g/mL) and the drugs used to treat tuberculosis. Complexes I and 2 also showed promising antitumor activity, with IC50 values of 0.46 +/- 0.02 and 0.43 +/- 0.08 mu M, respectively, against MDA-MB-231 breast tumor cells. (C) 2008 Elsevier Inc. All rights reserved.

A new nitrosyl ruthenium complex: Synthesis, chemical characterization, in vitro and in vivo antitumor activities and probable mechanism of action

This study describes the synthesis of a new ruthenium nitrosyl complex with the formula [RuCl(2)NO(BPA)] [BPA = (2-hydroxybenzyl)(2-methylpyridyl)amine ion], which was synthesized and characterized by spectroscopy, cyclic voltammetry, X-ray crystallography, and theoretical calculation data. The biological studies of this complex included in vitro cytotoxic assays, which revealed its activity against two different tumor cell lines (HeLa and Tm5), with efficacy comparable to that of cisplatin, a metal-based drug that is administered in clinical treatment. The in vivo studies showed that [RuCl2NO(BPA)] is effective in reducing tumor mass. Also, our results suggest that the mechanism of action of [RuCl(2)NO(BPA)] includes binding to DNA, causing fragmentation of this biological molecule, which leads to apoptosis. (C) 2011 Elsevier Masson SAS. All rights reserved.

Antimycobacterial and antitumor activities of Palladium(II) complexes containing isonicotinamide (isn): X-ray structure of trans-[Pd(N(3))(2)(isn)(2)]

Complexes of the type trans-[PdX(2)(isn)(2)] {X = Cl (1), N(3) (2), SCN (3), NCO (4); isn = isonicotinamide} were synthesized and evaluated for in vitro antimycobacterial and antitumor activities. The coordination mode of the isonicotinamide and the pseudohalide ligands was inferred by IR spectroscopy. Single crystal X-ray diffraction determination on 2 showed that coordination geometry around Pd(II) is nearly square planar, with the ligands in a trans configuration. All the compounds demonstrated better in vitro activity against Mycobacterium tuberculosis than isonicotinamide and pyrazinamide. Among the complexes, compound 2 was found to be the most active with MIC of 35.89 mu M. Complexes 1-4 were also screened for their in vitro antitumor activity towards LM3 and LP07 murine cancer cell lines. (C) 2010 Elsevier Masson SAS. All rights reserved.

Catecholase and DNase activities of copper(II) complexes containing phenolate-type ligands

Three new homodinuclear complexes containing substituted phenolate-type ligands based on the N(5)O(2) donor (2-(N,N-Bis(2-pyridylmethyl)aminomethyl)-6-(N`,N`-(2-hydroxybenzyl)(2-pyridylmethyl))aminomethyl)-4-methylphenol (H(2)L-H) were synthesized and characterized by X-ray crystallography. Potentiometric titration studies in 70% (v/v) aqueous ethanol show that all three complexes exhibit a common {Cu(II)(mu-phenoxo)(mu-OH)Cu(II)(OH)} core in solution. Kinetic studies on the oxidation reaction of 3,5-di-tert-butylcatechol revealed that the catalytic activity of the metal complexes increases toward the ligand containing an electron-donating group. In addition, these complexes also carried out DNA cleavage by hydrolytic and oxidative pathways. Copyright (C) 2010 John Wiley & Sons, Ltd.

Synthesis, characterization and cytotoxic activities of the [RuCl(2)(NO)(dppp)(L)]PF(6) complexes

The synthesis and characterization of ruthenium compounds of the type [RuCl(2)(NO)(dppp)(L)]PF(6) [dppp = 1,3-bis(diphenylphosphino)propane; L = pyridine, 4-methylpyridine, 4-phenylpyridine and dimethyl sulfoxide] are described. The complexes were characterized by elemental analysis, UV/Vis and infrared spectroscopy, cyclic voltammetry, and X-ray crystallography for the complexes with the pyridine and 4-methylpyridine ligands. In vitro evaluation of these nitrosyl complexes revealed cytotoxic activity from 7.1 to 19.0 mu M against the MDA-MB-231 breast tumor cells and showed that, in this case, they are more active than the reference metallodrug cisplatin. The 1,3-bis(diphenylphosphino)propane and the N-heterocyclic ligands alone failed to show cytotoxic activities at the concentrations tested (maximum concentration utilized = 200 mu M). (C) 2009 Elsevier Inc. All rights reserved.

Pt(II) and Ag(I) complexes with acesulfame: Crystal structure and a study of their antitumoral, antimicrobial and antiviral activities

Two new complexes of platinum(II) and silver(I) with acesulfame were synthesized. Acesulfame is in the anionic form acesulfamate (ace). The structures of both complexes were determined by X-ray crystallography. For K(2)[PtCl(2)(ace)(2)] the platinum atom is coordinated to two Cl(-) and two N-acesulfamate atoms forming a trans-square planar geometry. Each K(+) ion interacts with two oxygen atoms of the S(=O)(2) group of each acesulfamate. For the polymeric complex [Ag(ace)](n) the water molecule bridges between two crystallographic equivalent Agl atoms which are related each other by a twofold symmetry axis. Two Agl atoms, related to each other by a symmetry centre, make bond contact with two equivalent oxygen atoms. These bonds give rise to infinite chains along the unit cell diagonal in the ac plane. The in vitro cytotoxic analyses for the platinum complex using HeLa (human cervix cancer) cells show its low activity when compared to the vehicle-treated cells. The Ag(I) complex submitted to in vitro antimycobacterial tests, using the Microplate Alamar Blue (MABA) method, showed a good activity against Mycobacterium tuberculosis, responsible for tuberculosis, with a minimal inhibitory concentration (MIC) value of 11.6 mu M. The Ag(I) complex also presented a promising activity against Gram negative (Escherichia colt and Pseudomonas aeruginosa) and Gram positive (Enterococcus faecalis) microorganisms. The complex K(2)[PtCl(2)(ace)(2)] was also evaluated for antiviral properties against dengue virus type 2 (New Guinea C strain) in Vero cells and showed a good inhibition of dengue virus type 2 (New Guinea G strain) replication at 200 mu M, when compared to vehicle-treated cells. (C) 2010 Elsevier Inc. All rights reserved.

Total phenolic content and free radical scavenging activities of methanolic extract powders of tropical fruit residues

Methanolic extract powders of acerola, passion fruit and pineapple industrial residues, including pulp, seeds and peel, altogether (except for acerola) devoid of seeds, were screened for antioxidant capacity. The total phenolic contents (TPCs) of the extract powders were compared with their radical-scavenging activities (RSA) against both DPPH(center dot) and superoxide anion (O(2)(center dot-)) radicals, and their protective effect against liposome peroxidation, triggered by peroxyl radical. Lipid peroxidation was followed by the fluorescence decay of the probe, 4,4-difluoro-5-(4-phenyl-1,3-butadienyl)-4-bora-3a,4a-diaza-s-indacene-3-undecanoic acid (C(11)-BODIPY(581/591)). The TPCs of acerola, passion fruit and pineapple extract powders were (94.6 +/- 7.4); (41.2 +/- 4.2) and (9.1 +/- 1.3) mg of gallic acid equivalents g(-1) of dry extract, respectively. Acerola showed the best RSA-DPPH(center dot) scores, whereas passion fruit was more protective on the RSA-O(2)(center dot-) system. Together with the protective effects against lipid peroxidation (rate of BODIPY decay) which, were similar for acerola and passion fruit extracts, these data suggest that the methanolic extracts of acerola and passion fruit residues may be useful as antioxidant supplements, particularly the acerola extract, due to its high phenolic content. (C) 2008 Elsevier Ltd. All rights reserved

Base Excision Repair Activities Differ in Human Lung Cancer Cells and Corresponding Normal Controls

Oxidative damage to DNA is thought to play a role in carcinogenesis by causing Mutations, and indeed accumulation of oxidized DNA bases has been observed in samples obtained from tumors but not from surrounding tissue within the same patient. Base excision repair (BER) is the main pathway for the repair of oxidized modifications both in nuclear and mitochondrial, DNA. In order to ascertain whether diminished BER capacity might account for increased levels of oxidative DNA damage in cancer cells, the activities of BER enzymes in three different lung cancer cell lines and their non-cancerous counterparts were measured using oligonucleotide substrates with single DNA lesions to assess specific BER enzymes. The activities of four BER enzymes, OGG1, NTH1, UDG and APE1, were compared in mitochondrial and nuclear extracts. For each specific lesion, the repair activities were similar among the three cell lines used. However, the specific activities and cancer versus control comparison differed significantly between the nuclear and mitochondrial compartments. OGG1 activity, as measured by 8-oxodA incision, was upregulated in cancer cell mitochondria but down-regulated in the nucleus when compared to control cells. Similarly, NTH1 activity was also up-regulated in mitochondrial extracts from cancer cells but did not change significantly in the nucleus. Together, these results support the idea that alterations in BER capacity are associated with carcinogenesis.

Chemical Composition and Antimicrobial Activities of the Essential Oil of Hypericum cordatum (Vell. Conc.) N. Robson (Hypericaceae)

The volatile Constituents of the fresh materials of Hypericum cordatum were isolated by hydrodistillation kind analyzed by CC and GC/MS. The leaves produced 0.04% of a yellowish essential oil and the flowers did not. The main components of the oil were myrcene (40.18%), alpha-pinene (16.40%), and limonene (12%). The antibacterial activities of the oil against Saccharomyces aureus and Escherichia coli and the anti-fungal activities of the oil against the fungi Cladosporium cladosporioides and C. sphaerospemum were evaluated. The oil showed an antibacterial activity against the bacteria S. aureus and anti-fungal activity against the two fungi.

Antioxidant Capacity and Larvicidal and Antifungal Activities of Essential Oils and Extracts from Piper krukoffii

The leaves and twigs of Piper krukoffii, collected in the Carajas National Forest, north Brazil, yielded essential oils (2.0% and 0.8%), the main constituents of which were myristicin (40.3% and 26.7%), apiole (25.4% and 34.1%) and elemicin (2.8% and 3.0%). The antioxidant activities of the oils, methanol extract and its sub-fractions were evaluated. The DPPH EC(50) values varied from the ethyl acetate sub-fraction (73.4 +/- 3.7 mu g/mL) to the methanol extract (24.9 +/- 0.8 mu g/mL), and the ABTS TEAC values ranged in the same order from 265.7 to 349.2 mu Mol TE/g. These results indicated a significant antioxidant activity for the plant. The lignans (-)-kusunokin, yatein, (-)-hinokin and cubebin were identified in the methanol extract. The hydro-methanolic sub-fraction showed a high value for total phenol content (106.5 +/- 0.7 mg GAE/g), as well as (1)H NMR signals for sugar moieties. Crude extracts and sub-fractions were also able to inhibit beta-carotene bleaching, varying from 22.4 to 47.1%. The oils from the leaves and twigs showed strong larvicidal (21.4 and 3.6 mu g/mL) and fungicide (0.5 and 0.1 mu g/mL) activities.

Volsurf Descriptors to Analyse Anti-HCV and Cytotoxic Activities of Sesquiterpene Lactones from Asteraceae Family

Various significant anti-HCV and cytotoxic sesquiterpene lactones (SLs) have been characterized. In this work, the chemometric tool Principal Component Analysis (PCA) was applied to two sets of SLs and the variance of the biological activity was explored. The first principal component accounts for as much of the variability in the data as possible, and each succeeding component accounts for as much of the remaining variability as possible. The calculations were performed using VolSurf program. For anti-HCV activity, PC1 (First Principal Component) explained 30.3% and PC2 (Second Principal Component) explained 26.5% of matrix total variance, while for cytotoxic activity, PC1 explained 30.9% and PC2 explained 15.6% of the total variance. The formalism employed generated good exploratory and predictive results and we identified some structural features, for both sets, important to the suitable biological activity and pharmacokinetic profile.

Reduction of NO by CO on Cu/ZrO(2)/Al(2)O(3) catalysts: Characterization and catalytic activities

ZrO(2), gamma-Al(2)O(3) and ZrO(2)/gamma-Al(2)O(3)-supported copper catalysts have been prepared, each with three different copper loads (1, 2 and 5 wt%), by the impregnation method. The catalysts were characterized by nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR) with H(2), Raman spectroscopy and electronic paramagnetic resonance (EPR). The reduction of NO by CO was studied in a fixed-bed reactor packed with these catalysts and fed with a mixture of 1% CO and 1% NO in helium. The catalyst with 5 wt% copper supported on the ZrO(2)/gamma-Al(2)O(3) matrix achieved 80% reduction of NO. Approximately the same rate of conversion was obtained on the catalyst with 2 wt% copper on ZrO(2). Characterization of these catalysts indicated that the active copper species for the reduction of NO are those in direct contact with the oxygen vacancies found in ZrO(2). (C) 2009 Published by Elsevier Ltd.

Report on IEA Task-14 activities on solar collector systems conference in Rome, 25-29 Jan. 1993

The memebers of IEA (International Energy Agency) Task 14 (Advaced Active Solar Systems) met in Rome during January 1993. The latest developments in several countries were presented and discussed during this meeting. This report describes briefly the recent work carried out on small scale systems in the Domestic Hot Water (DHW) working group of Task 14, as reported by the representatives from Canada, Denmark, Germany, Holland and Switzerland. Klaus Lorenz, SERC, attended the meeting as observer and presented our work on small-tube heat exchangers. Several participants expressed their interest. A summary of his presentation is included in this report.