fac-/mer-[RuCl(3)(NO)(P-N)] (P-N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine): Synthesis, characterization and DFT calculations

Complex fac-[RuCl(3)(NO)(P-N)] (1) was synthesized from the reaction of [RuCl(3)(H(2)O)(2)(NO)] and the P-N ligand, o-[(N,N-dimethylamino)phenyl]diphenylphosphine) in refluxing methanol solution, while complex mer,trans-[RuCl(3)(NO)(P-N)] (2) was obtained by photochemical isomerization of (1) in dichloromethane solution. The third possible isomer mer, cis-[RuCl(3)(NO)(P-N)] (3) was never observed in direct synthesis as well as in photo-or thermal-isomerization reactions. When refluxing a methanol solution of complex (2) a thermally induced isomerization occurs and complex (1) is regenerated. The complexes were characterized by NMR ((31)P{(1)H}, (15)N{1H} and 1H), cyclic voltammetry, FTIR, UV-Vis, elemental analysis and X-ray diffraction structure determination. The (31)P{(1)H} NMR revealed the presence of singlet at 35.6 for (1) and 28.3 ppm for (2). The (1)H NMR spectrum for (1) presented two singlets for the methyl hydrogens at 3.81 and 3.13 ppm, while for (2) was observed only one singlet at 3.29 ppm. FTIR Ru-NO stretching in KBr pellets or CH(2)Cl(2) solution presented 1866 and 1872 cm(-1) for (1) and 1841 and 1860 cm(-1) for (2). Electrochemical analysis revealed a irreversible reduction attributed to Ru(II)-NO(+) -> Ru(II)-NO(0) at -0.81 V and -0.62 V, for (1) and (2), respectively; the process Ru(II) -> Ru(III), as expected, is only observed around 2.0 V, for both complexes. Studies were conducted using (15)NO and both complexes were isolated with (15)N-enriched NO. Upon irradiation, the complex fac-[RuCl(3)(NO)(P-N)] (1) does not exchange (14)NO by (15)NO, while complex mer, trans-[RuCl(3)(NO)(P-N)] (2) does. Complex mer, trans-[RuCl(3)((15)NO)(P-N)] (2`) was obtained by direct reaction of mer, trans-[RuCl(3)(NO)(P-N)] (2) with (15)NO and the complex fac-[RuCl(3)((15)NO)(P-N)] (1`) was obtained by thermal-isomerization of mer, trans-[RuCl(3)((15)NO)(P-N)] (2`). DFT calculation on isomer energies, electronic spectra and electronic configuration were done. For complex (1) the HOMO orbital is essentially Ru (46.6%) and Cl (42.5%), for (2) Ru (57.4%) and Cl (39.0%) while LUMO orbital for (1) is based on NO (52.9%) and is less extent on Ru (38.4%), for (2) NO (58.2%) and Ru (31.5%). (C) 2011 Elsevier B. V. All rights reserved.

Raman spectra of a pseudo-oxocarbon anion in ionic liquids

Raman and electronic spectra of the [3,5-bis(dicyanomethylene)cyclopentane-1,2,4-trionate] dianion, the croconate violet (CV), are reported in solutions of ionic liquids based on imidazolium cations. Different normal modes of the CV anion, nu (C=O), nu (CO) + nu (CC) + nu (CCN), and nu(C N), were used as probes of solvation characteristics of ionic liquids, and were compared with spectra of CV in common solvents. The spectra of CV in ionic liquids are similar to those in dichloromethane solution, but distinct from those in protic solvents such as ethanol or water. The UV-vis spectra of CV in ionic liquids strongly suggest pi-pi interactions between the CV anion and the imidazolium cation. Copyright (C) 2009 John Wiley & Sons, Ltd.

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4`-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 degrees C. UV-vis analysis revealed an E-gap of 3.5 eV Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested. (c) 2008 Elsevier B.V. All rights reserved.

Mutagenicity and DNA adduct formation of PAH, nitro-PAH, and oxy-PAH fractions of atmospheric particulate matter from Sao Paulo, Brazil

Urban particulate matter (UPM) contributes to lung cancer incidence. Here, we have studied the mutagenic activity and DNA adduct-forming ability of fractionated UPM extractable organic matter (EOM). UPM was collected with a high-volume sampler in June 2004 at two sites, one at street level adjacent to a roadway and the other inside a park within the urban area of the city of Sao Paulo, Brazil. UPM was extracted using dichloromethane, and the resulting EOM was separated by HPLC to obtain PAH, nitro-PAH, and oxy-PAH fractions which were tested for mutagenicity with the Salmonella strains TA98 and YG1041 with and without S9 metabolic activation. The PAH fraction from both sites showed negligible mutagenic activity in both strains. The highest mutagenic activity was found for the nitro-PAH fraction using YG1041 without metabolic activation; however, results were comparable for both sites. The nitro-PAH and oxy-PAH fractions were incubated with calf thymus DNA under reductive conditions appropriate for the activation of nitro aromatic compounds, then DNA adduct patterns and levels were determined with thin-layer chromatography (TLC) (32)p-postlabeling method using two enrichment procedures-nuclease PI digestion and butanol extraction. Reductively activated fractions from both sites produced diagonal radioactive zones (DRZ) of putative aromatic DNA adducts on thin layer plates with both enrichment procedures. No such DRZ were observed in control experiments using fractions from unexposed filters or from incubations without activating system. Total adduct levels produced by the nitro-PAH fractions were similar for both sites ranging from 30 to 45 adducts per 10(8) normal nucleotides. In contrast, the DNA binding of reductively activated oxy-PAH fractions was three times higher and the adduct pattern consisted of multiple discrete spots along the diagonal line on the thin layer plates. However, DNA adduct levels were not significantly different between the sampling sites. Both samples presented the same levels of mutagenic activity. The response in the Salmonella assay was typical of nitroaromatics. Although, more mutagenic activity was related to the nitro-PAH fraction in the Salmonella assay, the oxy-PAH fractions showed the highest DNA adduct levels. More studies are needed to elucidate the nature of the genotoxicants occurring in Sao Paulo atmospheric samples. (C) 2008 Elsevier B.V. All rights reserved.

Antiparasitic activity of biochanin A, an isolated isoflavone from fruits of Cassia fistula (Leguminosae)

The fractionation through bioguided antileishmanial activity of the dichloromethane extract of Cassia fistula fruits (Leguminosae) led to the isolation of the active isoflavone biochanin A, identified by spectroscopic methods. This compound showed 50% effective concentration (EC(50)) value of 18.96 mu g/mL against promastigotes of Leishmania (L.) chagasi. The cytotoxicity of this substance against peritoneal macrophages resulted in an EC(50) value of 42.58 mu g/mL. Additionally, biochanin A presented an anti-Trypanosoma-cruzi activity, resulting in an EC(50) value of 18.32 mu g/mL and a 2.4-fold more effectiveness than benznidazole. These results contribute with novel antiprotozoal compounds for future drug design studies.

TLC Separation and Identification of the Essential Oil Constituents from Aloysia gratissima

The present work had as objective the isolation of the five compounds by thin-layer Chromatography (TLC) from the essential oil of the Aloysia gratissima. For this, a number of systems of eluents were used for its separation, indicating that through the system acetone/hexane in proportions (v/v) 1:30 it was possible to isolate guaiol, elemol, pinocanphone (trans-3-pinanone), cis-pinocarvyl, and acorenone. The isolation of the compound acorenone from the other compounds was possible with the mixture of solvents hexane/dichloromethane in proportions (v/v) (1:1,3).

Bis(1-naphthyl) telluride

Yellow crystals of the title compound, C₂₀H₁₄Te, were obtained serendipitously in an attempt to recrystallize the reduction product of (1-C₁₀H₇)[(CH(Me)COC₆H₅)]TeCl₂ from dichloromethane. The molecule exhibits an angular geometry with almost equal Te-C_aryl bonds and a C-Te-C angle close to values observed for other diaryl tellurides. One of the aromatic ring systems lies in the C-Te-C plane and the other is oriented at 76.81 (6)°, giving an almost T-shaped conformation that is compatible with the steric demand of 1-naphthyl ligands.

Studies on the behaviour of polystyrene in reversed phase chromatography

Polystyrene behaviour in reversed phase high performance liquid chromatography was influenced mainly by the solvent system, but secondary affects were observed depending on the stationary phase. A variety of reversed phase columns were investigated using mobile phase combinations of dichlorom ethane-methanol, dichloromethane-acetonitrile, ethyl acetate-methanol and ethyl acetate-acetonitrile. Several different modes of behaviour were observed depending on the polymer solubility in the solvent system. In the dichloromethane-methanol solvent system, polymer-stationary phase interactions only occurred when the molecules had pore access. Retention of excluded polystyrene depended on the kinetics of precipitation and redissolution of the polymer. Peak splitting and band broadening occurred when the kinetics were slow and molecular weight separations were limited !o oligomers and polystyrenes lower than 5-10(4) dalton. Excellent molecular weight separations of polystyrenes were obtained using gradient elution reversed phase chromatography with a dichloromethane-acetonitrile mobile phase on C18 columns. The retention was based on polymer-stationary phase interactions regardless of the column pore size. Separations were obtained on large diameter pellicular adsorbents that were almost as good as those obtained on porous adsorbents, showing that pore access was not essential for the retention of high molecular weight polystyrenes. In the best example, the separation ranged from the monomer to 10(6) dalton in a single analysis. Very little adsorption of excluded polymers was observed on C8 or phenyl columns. Polystyrene molecular weight separations to 7-10(5) dalton were obtained in an ethyl acetate-acetonitrile solvent system on C18 columns. Adsorption was responsible for retention. When an ethyl acetate-methanol solvent system was used, no molecular weight separations were obtained because of complex peak splitting. Reversed phase chromatography was compared to size exclusion chromatography for the analysis of polydisperse polystyrenes. Similar results were obtained using both methods. However, the reversed phase method was less sensitive to concentration effects and gave better resolution.

Synthesis, X-ray structure and electrochemical characterization of palladium(II) bearing ferrocenyldiphenylphosphine complexes

Four new complexes, [PdX(κ2-2-C6R4PPh2)(PPh2Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh2Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ2-2-C6F4PPh2)(μ-I)(μ-2-C6F4PPh2)PdI(PPh2Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected. The cis/trans ratio of 1–4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh2Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh2Fc; subsequently, the metal–phosphorus bond is cleaved, leading to free PPh2Fc+, which undergoes further chemical and electrochemical reactions.

Ionic liquid effects on the redox potential of ferrocene

The ionic liquid, IL, dependence of the mid-point potential of the ferrocene|ferrocenium, Fc^0/+, couple versus the decamethylferrocene|decamethylferrocenium, DmFc^0/+, couple was studied in eleven ILs and in dichloromethane with added IL as the supporting electrolyte. The difference in mid-point potential between Fc and DmFc indicates that Fc^0/+ couple is clearly dependent on the IL structure. A variation of about 0.100 V over the range of ILs studied under neat conditions and by ca. 0.050 V when studied in dichloromethane is reported. Meanwhile, a variable potential shift ranging from 0.014 to 0.082 V was observed when data was compared in these two systems (ILs vs. dichloromethane). The effect of water and lithium ion on the Fc^0/+ and DmFc^0/+ redox potential was also evaluated and found to be minimal.

Electrosprayed PLGA smart containers for active anti-corrosion coating on magnesium alloy Amlite

A novel self-healing system, consisting of poly(lactic-co-glycolic) acid (PLGA) porous particles loaded with a corrosion inhibitor, i.e. benzotriazole (BTA), has been successfully achieved via direct electro-spray deposition and subsequent epoxy spraying upon magnesium (Mg) alloy AMlite. The two-step process greatly simplified the multi-step fabrication of smart coatings reported previously. The PLGA particles demonstrate rapid response to both water and pH increase incurred by corrosion of Mg, ensuring instant and ongoing release of BTA to self-heal the protective functionality and retard further corrosion. Furthermore, nanopores in the PLGA–BTA microparticles, formed by the fast evaporation of dichloromethane during the electrospray process, also contribute to the fast release of BTA. Using Mg alloy AMlite as a model substrate which requires corrosion protection, potentiodynamic polarisation characterisation and scratch testing were adopted to reveal the anti-corrosion capability of the active coating.

Aggregation of a dibenzo[b,def]chrysene based organic photovoltaic material in solution

Detailed electrochemical studies have been undertaken on molecular aggregation of the organic semiconductor 7,14-bis((triisopropylsilyl)-ethynyl) dibenzo[b,def]chrysene (TIPS-DBC), which is used as an electron donor material in organic solar cells. Intermolecular association of neutral TIPS-DBC molecules was established by using 1H NMR spectroscopy as well as by the pronounced dependence of the color of TIPS-DBC solutions on concentration. Diffusion limited current data provided by near steady-state voltammetry also reveal aggregation. Furthermore, variation of concentration produces large changes in shapes of transient DC and Fourier transformed AC (FTAC) voltammograms for oxidation of TIPS-DBC in dichloromethane. Subtle effects of molecular aggregation on the reduction of TIPS-DBC are also revealed by the highly sensitive FTAC voltammetric method. Simulations of FTAC voltammetric data provide estimates of the kinetic and thermodynamic parameters associated with oxidation and reduction of TIPS-DBC. Significantly, aggregation of TIPS-DBC facilitates both one-electron oxidation and reduction by shifting the reversible potentials to less and more positive values, respectively. EPR spectroscopy is used to establish the identity of one-electron oxidized and reduced forms of TIPS-DBC. Implications of molecular aggregation on the HOMO energy level in solution are considered with respect to efficiency of organic photovoltaic devices utilizing TIPS-DBC as an electron donor material. © 2014 American Chemical Society.

Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)]

Characterization of the anticancer active compound trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one-electron-oxidized Pt^III derivative. The square-planar organoamidoplatinum(II) compound was synthesized through a carbon dioxide elimination reaction. Structural characterization by using single-crystal X-Ray diffraction reveals a trans configuration with respect to donor atoms of like charges. As Pt^III intermediates have been implicated in the reactions of platinum anticancer agents, electrochemical conditions favoring the formation of one-electron-oxidized species were sought. Transient cyclic voltammetry at fast scan rates or steady-state rotating disc and microelectrode techniques in a range of molecular solvents and an ionic liquid confirm the existence of a well-defined, chemically and electrochemically reversible one-electron oxidation process that, under suitable conditions, generates a Pt^III complex, which is proposed to be monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Electron paramagnetic resonance spectra obtained from highly non-coordinating dichloromethane/([Bu4N][B(C6F5)4]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the Pt^III assignment rather than formation of a Pt^II cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}- Cl(py)], and the solvent/electrolyte. In the low-polarity solvent CH2Cl2 containing the very weakly coordinating electrolyte [Bu4N][B(C6F5)4], a well-defined reversible one-electron oxidation process is observed on relatively long timescales, which is consistent with the stabilization of the cationic platinum(III) complex in non-coordinating media. Bulk electrolysis of low concentrations of [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] favors the formation of monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Simulations allow the reversible potential of the Pt^II/Pt^III process and the diffusion coefficient of [Pt^III{(p-BrC6F4)- NCH2CH2NEt2}Cl(py)]⁺ to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.

Phase inversion of ionomer-stabilized emulsions to form high internal phase emulsions (HIPEs)

Herein, we report the phase inversion of ionomer-stabilized emulsions to form high internal phase emulsions (HIPEs) induced by salt concentration and pH changes. The ionomers are sulfonated polystyrenes (SPSs) with different sulfonation degrees. The emulsion types were determined by conductivity measurements, confocal microscopy and optical microscopy, and the formation of HIPE organogels was verified by the tube-inversion method and rheological measurements. SPSs with high sulfonation degrees (water-soluble) and low sulfonation degrees (water-insoluble) can stabilize oil-in-water emulsions; these emulsions were transformed into water-in-oil HIPEs by varying salt concentrations and/or changing the pH. SPS, with a sulfonation degree of 11.6%, is the most efficient, and as low as 0.2 (w/v)% of the organic phase is enough to stabilize the HIPEs. Phase inversion of the oil-in-water emulsions occurred to form water-in-oil HIPEs by increasing the salt concentration in the aqueous phase. Two phase inversion points from oil-in-water emulsions to water-in-oil HIPEs were observed at pH 1 and 13. Moreover, synergetic effects between the salt concentration and pH changes occurred upon the inversion of the emulsion type. The organic phase can be a variety of organic solvents, including toluene, xylene, chloroform, dichloroethane, dichloromethane and anisole, as well as monomers such as styrene, butyl acrylate, methyl methacrylate and ethylene glycol dimethacrylate. Poly(HIPEs) were successfully prepared by the polymerization of monomers as the continuous phase in the ionomer-stabilized HIPEs.

Análise química e avaliação da atividade antiviral de hypericum connatum lam.

Plantas da família Guttiferae apresentam diversas atividades biológicas sendo Hypericum o gênero mais importante devido às atividades antidepressiva, antibacteriana e antiviral de algumas espécies. Hypericum connatum, utilizado no sul do Brasil para o tratamento de feridas de boca, demonstrou atividade contra o lentivírus, responsável pela imunodeficiência felina. Objetivo: isolar e identificar as substâncias majoritárias de H. connatum e testar a atividade de extratos obtidos das partes aéreas e raízes e das substâncias isoladas frente a duas cepas do herpesvírus simples tipo 1 (HSV-1). Método: foram obtidos frações nhexano, diclorometano e metanol e extratos bruto, aquosos a diferentes temperaturas e hidro-etanólico das partes aéreas e raízes. As frações n-hexano e metanólica das partes aéreas foram submetidas à coluna cromatográfica para o isolamento de substâncias. Os extratos e substâncias isoladas foram testados frente ao HSV-1, cepas KOS e ATCC-VR733. Determinou-se a concentração máxima não tóxica (CMNT) à célula e a concentração que provoca alteração morfológica em 50% das células (CC50) pela técnica da alteração morfológica celular, utilizando-se células VERO, linhagem ATCC CCL-81. A avaliação da atividade antiviral foi realizada em placas de microtitulação e medida pela inibição do efeito citopático (ECP) provocado pelo vírus. Resultados e Conclusões: da fração n-hexano foi isolado hiperbrasilol B, da fração metanólica foram isolados amentoflavona, hiperosídeo e guaijaveriana, além de um flavonol de estrutura ainda não definida (HCN3). A fração n-hexano e o extrato bruto das raízes inibiram o ECP das cepas KOS e ATCC-VR733. Os demais extratos testados não apresentaram atividade antiviral. Dentre as substâncias analisadas, hiperbrasilol B, amentoflavona e HCN3 foram ativos frente às duas cepas. Os flavonóides hiperosídeo e guaijaverina não apresentaram atividade anti-HSV-1.