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A family of stilbenyl-azopyrroles compounds 2a-d and 3a-d was efficiently obtained via a Mizoroki-Heck C-C-type coupling reaction between 2-(4'-iodophenyl-azo)-N-methyl pyrrole (1a) and different vinyl precursors. The influence of the π-conjugated backbone and the effect of the pyrrole moiety were correlated with their optical properties. Studies via UV-Visible spectrophotometry revealed that the inclusion of EWG or EDG favors a red-shift of the main absorption band in these azo compounds compared with their non-substituted analogues. Furthermore, there is a clear influence between the half-life of the Z isomer formed by irradiation with white light and the push-pull behavior of the molecules. In several cases, the stilbenyl-azopyrroles led to the formation of J-type aggregates in binary MeOH : H2O solvents, which are of interest for water compatible applications.

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We herein report the synthesis and catalytic application of a new family of dinuclear Cu(I) complexes based on [N,P]-pyrrole ligands. The Cu(I) complexes (4a-d) were obtained in good yields and their catalytic properties were evaluated in the1,3-dipolar cycloaddition of azomethine ylides and electron-deficient alkenes. The air-stable complexes 4a-d exhibited high endo-diasteroselectivity to obtain substituted pyrrolidines, and the catalytic system showed excellent reactivity and wide substitution tolerance.

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Reaction of complex [TpMe2Ir(η4-CH2C(Me)C(Me)C2)] (1) with a series of aromatic ketones at 130 °C renders, by means of a selective ortho-CH activation, Ir(III)-metallacycles 2-5, which display an Ir-H bond. When [TpMe2Ir(C6H5)2N2] (6) is treated with 2-(trifluoromethyl)acetophenone and 2-fluoroacetophenone at 80 °C, the formation of dimeric (7) and trimeric architectures (8) is achieved through the meta- and para-CH activation of the aromatic ketone, respectively. The generation of complexes 2-5 is proposed to occur by the initial formation of Ir(III) η1-ketone adducts as key intermediates, followed by aromatic CH activations and the release of a butadiene ligand. The formation of complexes 7 and 8 involves an assisted process in which a metal center activation of the less sterically hindered C-H bond of the aromatic ketone takes place (releasing a benzene molecule), followed by the coordination of the carbonyl group, which generates the respective dimeric and trimeric structures. Complexes 7 and 8 are efficient catalysts for the transfer hydrogenation of ketones and aldehydes using isopropanol as the hydrogen source. All complexes have been fully characterized by NMR spectroscopy, FT-IR, elemental analysis and, in the cases of 7 and 8, X-ray crystallography. Details of the reaction conditions, isolation of the products, and proposals for the pathways of formation of complexes 2-5 and 7-8 are discussed.

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The synthesis of a series of ferrocenylvinylketenes as stable η4-[Fe(CO)3] complexes (3a-f) was successfully accomplished through the reaction of η2-[Fe(CO)4] complexes under mild carbonylation conditions. The reactivity of 3a-f under thermal conditions afforded the unexpected formation of a novel family of (µ2,η3-allyl-η5-oxapentadienyl)diiron pentacarbonyl complexes 5a-f proposed to be formed by a sequence metathesis-haptotropic rearrangement between the starting η4-vinylketene iron(0) complex 3 and a η4-vinylcarbene iron(0) complex trapped in situ after a reversible carbonylation process favored by the thermal conditions. An electron density distribution analysis (EDD) of 5e using high-resolution X-ray diffraction data in combination with the DFT framework was performed to understand the electronic communication between the two iron fragments.

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Iodine promotes the in situ formation of iron(II) species from η4-vinylketene[Fe(CO)3] (3a-h) as a key intermediate for the synthesis of 2(5H)-furanones (4a-h) by a sequential water-insertion/carbon-oxygen coupling under mild reaction conditions. Compounds 4a-h were obtained in good to excellent yields. A possible reaction pathway was also proposed by DFT calculations. This methodology can be extended to the synthesis of (5H)-pyrrol-2-ones using anilines, with moderate yields and a few limitations.

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2-Thiazolines are important building blocks in organic synthesis and are of great importance in many areas of chemistry. At the end of the last century, the use of 2-thiazolines increased in a significant way, especially in synthesis and catalysis. This review highlights the synthetic and catalytic value of 2-thiazolines in the last two decades. We will discuss the new synthetic methodologies for obtaining these heterocycles including new schemes for accessing their asymmetric versions. Most of the new catalytic applications include a variety of 2-thiazoline ligands containing diverse donor atoms, which in combination with metals like Pd, Ir, and Cu, among others, exhibit remarkable catalytic performances.

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We present a new design for non-linear optically responsive molecules based on a modular scheme where a polymethinic antenna section with important two-photon absorption properties is bonded to an isomerizable actuator section composed of a stilbenyl-azopyrrole unit. Upon two photon excitation, energy migration from the antenna-localized second singlet excited state to the stilbenyl-azopyrrole section allows for efficient indirect excitation and phototransformation of this actuator.

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AIM: The aim of this study was to assess treatment modalities, treatment response, toxicity profile, disease progression and outcomes in 14 patients with a confirmed diagnosis of primary cutaneous T-cell lymphoma (PCTCL) treated with total skin electron beam therapy (TSEBT). BACKGROUND: Primary cutaneous lymphomas (PCLs) are extranodal non-Hodgkin lymphomas originating in the skin without evidence of extracutaneous disease at diagnosis. Despite advances in systemic and local therapy options, the management of advanced stages remains mostly palliative. MATERIALS AND METHODS: This is a retrospective study of patients with PCTCL, diagnosed and treated in a reference center in Mexico City, analyzing treatment modalities, response to treatment, long-term outcome, and mortality. RESULTS: Eight males (57%) and 6 (43%) females were identified. Most patients were stage IVA (n = 5, 36%) followed by stage IB and IIB (28.5% and 21.4%, respectively). Eleven patients received the low-dose RT scheme (12 Gy), 1 patient, the intermediate-dose RT scheme (24 Gy), and 2 patients, the conventional-dose RT scheme (36 Gy). Mean follow-up time was 4.6 years. At first follow-up examination, 6-8 weeks after radiotherapy, the overall response rate (ORR) for the cohort was 85%. The median PFS for the whole cohort was 6 months. CONCLUSION: This study reinforces the role of TSEBT when compared with other treatment modalities and novel agents. Low-dose TSEBT is now widely used because of the opportunity for retreatment.

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A new family of push-pull biphenyl-azopyrrole compounds 3b-g and 4b-d was efficiently obtained via a Suzuki cross-coupling reaction between 2-(4'-iodophenyl-azo)-N-methyl pyrrole (1a) or 3-(4'-iodophenyl-azo)-1,2,5-trimethyl pyrrole (2a) and 4'-substituted phenyl boronic acids in excellent yields. The influence of the π-biphenyl backbone and pyrrole pattern substitution was correlated with their optical properties. Solvatochromic studies via UV-visible spectrophotometry revealed that the inclusion of a 4'-nitro-biphenyl fragment favors a red-shift of the main absorption band in these azo compounds compared with their non-substituted analogues. Likewise, optical band-gaps were estimated by means of electronic absorption spectra and correlated with TD-DFT studies. The pyrrole pattern substitution and the π-conjugated backbone exhibit a clear influence on their thermal isomerization kinetics at room temperature. In all cases, biphenylazo-pyrrole compounds lead to the formation of J-type aggregates in binary MeOH : H2O solvents. Under these conditions, compounds 3b-c undergo a water-assisted cis-to-trans isomerization at room temperature.

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A set of alkyl aluminum complexes supported by non-symmetric ferrocenyl amidine ligands were used as catalysts for the preparation of cyclic carbonates from epoxides and carbon dioxide using Bu4NI as a co-catalyst. A modified method for the synthesis of aminoferrocene allowed us to obtain this precursor in quantitative yield. Treatment of aminoferrocene with the corresponding acetimidoyl chloride afforded the desired ferrocenyl amidine ligands L1H, (E)-N-(2,6-diisopropylphenyl)-N'-(ferrocenyl)acetimidamide, and L2H, (E)-N-(2,6-dimethylphenyl)-N'-(ferrocenyl)acetimidamide. The reaction of these ligands with 1.0 or 0.5 equiv. of AlMe3 led to the synthesis of aminoferrocene based aluminum complexes ((L1)AlMe2 (1), (L2)AlMe2 (2), (L1)2AlMe (3), and (L2)2AlMe (4)) in excellent yields, which were characterized by spectroscopic and X-ray diffraction methods. In addition, we have studied their electrochemical properties and complex 1 was found to be the most active catalyst for the formation of cyclic carbonates 6a-j from their corresponding epoxides 5a-j and CO2.

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AIMS: A major drawback of using dairy slurry as fertilizer is that it may contains pathogens such as Mycobacterium avium subsp. paratuberculosis (MAP), and it could represent a risk to animal and public health. Thus, the aim of this study was to evaluate the fate of MAP and bacterial communities in dairy slurry after chemical treatments. METHODS AND RESULTS: Cattle slurry, naturally contaminated with MAP, was collected from a dairy herd and divided into 32 glass bottles which were assigned to eight different treatments (control, 3·0% CaO, 0·5% NaOH; 0·087%, 0·11% and 0·14% H2 SO4 ; and 1·0 and 2·5% KMnO4 ). Treated dairy slurry samples were evaluated at 0, 1, 3, 7, 15, 30 and 60-days following treatment application for viable MAP and dairy slurry pH, and in addition temperature in this material was monitored continuously. Bacterial counts were estimated at each sampling time. A Bayesian zero-inflated Poisson mixed model was fitted to assess the effect of each treatment on the count of MAP cells. Model results indicated that only the 3·0% CaO treatment had a statistically important negative effect on MAP counts during the study period. For most treatments, MAP was undetectable immediately after chemical treatment but re-appeared over time, in some replicates at low concentrations. However, in those cases MAP counts were not statistically different than the control treatment. Regarding the fate of the other bacterial populations, the Firmicutes phylum was the dominant population in the un-treated slurry while Clostridia class members were among the most prevalent bacteria after the application of most chemical treatments. CONCLUSION: Only 3% CaO treatment had a statistically important negative effect on MAP viability in cattle slurry. SIGNIFICANCE AND IMPACT OF THE STUDY: This study provides evidence of MAP partial control in dairy slurry. This information should be considered as a best management practice to reduce MAP and other pathogens for slurry management on dairy farms.

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An efficient method to obtain chiral 1,2-disubstituted ferrocenyl ligands has been developed. The introduction of planar chirality was accomplished by using 2-thiazoline as an ortho-directing lithiation group, and moreover, these kinds of ligands possess a central chirality from the amino alcohol used in their synthesis. The X-ray analysis and DFT calculations confirmed the diastereoselectivity of ortho-lithiation and the configuration of the planar chirality. The ability of these new bidentate [N,S]-ferrocene ligands to act in Pd-catalyzed asymmetric allylic alkylation has also been demonstrated and compared with their oxazoline counterparts.

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The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO)5NH(CH2)15CH3, where R is a ferrocenyl 2(a-b) or a phenyl 4(a-b) group as a donor moiety and a Fischer carbene of chromium (0) or tungsten (0) as an acceptor group, are reported. These four push-pull systems formed Langmuir (L) monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves); Brewster angle microscopic images were also obtained. By using the Langmuir-Blodgett (LB) method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl)(hexadecylamine)methylidene] pentacarbonyl tungsten (0) are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices.

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Internal dosimetry intercomparisons are essential for the verification of applied models and the consistency of results'. To that aim, the First Regional Intercomparison was organised in 2005, and that results led to the Second Regional Intercomparison Exercise in 2013, which was organised in the frame of the RLA 9/066 and coordinated by Autoridad Regulatoria Nuclear of Argentina. Four simulated cases covering intakes of (131)I, (137)Cs and Tritium were proposed. Ninteen centres from thirteen different countries participated in this exercise. This paper analyses the participants' results in this second exercise in order to test their skills and acquired knowledge, particularly in the application of the IDEAS Guidelines. It is important to highlight the increased number of countries that participated in this exercise compared with the first one and, furthermore, the improvement in the overall performance. The impact of the International Atomic Energy Agency (IAEA) Projects since 2003 has led to a significant enhancement of internal dosimetry capabilities that strengthen the radiation protection of workers.

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The synthesis and characterization of five metal complexes derived from sodium meclofenamate (1) are reported: [Cd(C14H10NO2Cl2)2∙(CH3OH)]n∙nCH3OH (6), [Pb(C14H10NO2Cl2)2]n (7), [Co(C14H10NO2Cl2)]n (8), [Cu(C14H10NO2Cl2)]n (9), and [Cu(C14H10NO2Cl2)2(C5H5N)2] (10) (C14H10NO2Cl2=meclofenamate; C5H5N=pyridine). The characterization of the compounds was based on FTIR and UV-visible spectroscopy, mass spectrometry and, in the case of complexes 6 and 10, single crystal X-ray diffraction analysis. For compound 6, the structural analysis revealed a 1-D polymeric chain structure, in which pentagonal planar [Cd(RCOO)2(CH3OH)] units were linked through bridging carboxylate functions of the meclofenamate ligands. The overall coordination environment of the Cd(II) ions was seven-coordinate, since each carboxylate group exhibited a µ3-bridging coordination mode. On the other hand, for complex 10 a discrete mononuclear structure was observed, in which the six-coordinate copper(II) metal atoms were coordinated by two pyridine molecules and the carboxylate functions of two meclofenamate entities, in an anisobidentate coordination mode. The antibacterial activity of compounds 6-9 against four strains of Gram positive (Staphylococcus aureus and Bacillus subtilis) and Gram negative (Escherichia coli and Pseudomonas aeruginosa) bacteria was examined, finding that only complex 6 was active. Additionally, it was found that the Co(II) and Cu(II) complexes 8 and 9 showed peroxidase activity.

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The study assessed the effect of soil slope on Mycobacterium avium subsp. paratuberculosis transport into rainwater runoff from agricultural soil after application of M. avium subsp. paratuberculosis-contaminated slurry. Under field conditions, 24 plots of undisturbed loamy soil 1 by 2 m(2) were placed on platforms. Twelve plots were used for water runoff: 6 plots at a 3% slope and 6 plots at a 15% slope. Half of the plots of each slope were treated with M. avium subsp. paratuberculosis-contaminated slurry, and half were not treated. Using the same experimental design, 12 plots were established for soil sampling on a monthly basis using the same spiked slurry application and soil slopes. Runoff following natural rainfall was collected and analyzed for M. avium subsp. paratuberculosis, coliforms, and turbidity. M. avium subsp. paratuberculosis was detected in runoff from all plots treated with contaminated slurry and one control plot. A higher slope (15%) increased the likelihood of M. avium subsp. paratuberculosis detection but did not affect the likelihood of finding coliforms. Daily rainfall increased the likelihood that runoff would have coliforms and the coliform concentration, but it decreased the M. avium subsp. paratuberculosis concentration in the runoff. When there was no runoff, rain was associated with increased M. avium subsp. paratuberculosis concentrations. Coliform counts in runoff were related to runoff turbidity. M. avium subsp. paratuberculosis presence/absence, however, was related to turbidity. Study duration decreased bacterial detection and concentration. These findings demonstrate the high likelihood that M. avium subsp. paratuberculosis in slurry spread on pastures will contaminate water runoff, particularly during seasons with high rainfall. M. avium subsp. paratuberculosis contamination of water has potential consequences for both animal and human health.

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We perform a bidimensional analysis to evaluate the variation of the fluorescence decay of europium thenoyltrifluoroacetonate (EuTTA) with temperature changes. We analyze how a specific thermal distribution modifies the spatial temperature of the sensing film and we study the corresponding fluorescence response using an integral functional of the emission decay. We present experimental results of a thermal distribution registered with the EuTTA-based thermal-to-visible conversion method. Furthermore, we analyze the spatial and temporal response of the proposed sensing element by using heat-transfer theory. Based on the presented analysis, we establish the optimal thermal and physical design for the sensing element of the proposed thermal-to-visible converter.

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There are over one million hectares of pasture in Chile, and 80% and 50% of the country's milk and meat comes from 72% of this area, situated in the lake region of southern Chile. The soils are volcanic and a major characteristic is that they have very high organic matter (OM) contents with the potential to support plant growth with only moderate levels of added nitrogen (N). To understand better the potential fertility of these soils in order to maximise production and minimise losses of N, we undertook studies using the stable isotope of N ((15)N) to resolve the rates of the main internal N cycling processes in three soils representing the two main volcanic soil types: Osorno and Chiloé (Andisol) and Cudico (Ultisol). We also assessed the longer-term potential of these soils to sustain N release using anaerobic incubation. Gross rates (µg N g(-1) day(-1)) of mineralisation were 27.9, 27.1 and 15.5 and rates of immobilisation were 5.9, 12.0 and 6.3 for Osorno, Chiloé and Cudico, respectively, implying high rates of net mineralisation in these soils. This was confirmed by anaerobic incubation which gave potential seasonal net mineralisation indices of 1225, 1059 and 450 kg N ha(-1) in the top 10 cm soil layers of the three soils. However, plant production may still benefit from added N, as the release of N from organic sources may not be closely synchronised with crop demand. The low rates of nitrification that we found with these acidic soils suggest that the more mobile N (viz. nitrate-N) would be in limited supply and plants would have to compete for the less mobile ammonium-N with the soil microbial biomass. Nitrogen was mineralised in appreciable amounts even down to 60 cm depth, so that leaching could become significant, particularly if the soils were limed, which could enhance nitrification and N mobility through the soil profile.

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Details regarding the fate of Mycobacterium avium subsp. paratuberculosis (basonym, Mycobacterium paratuberculosis) after manure application on grassland are unknown. To evaluate this, intact soil columns were collected in plastic pipes (lysimeters) and placed under controlled conditions to test the effect of a loamy or sandy soil composition and the amount of rainfall on the fate of M. paratuberculosis applied to the soil surface with manure slurry. The experiment was organized as a randomized design with two factors and three replicates. M. paratuberculosis-contaminated manure was spread on the top of the 90-cm soil columns. After weekly simulated rainfall applications, water drainage samples (leachates) were collected from the base of each lysimeter and cultured for M. paratuberculosis using Bactec MGIT ParaTB medium and supplements. Grass was harvested, quantified, and tested from each lysimeter soil surface. The identity of all probable M. paratuberculosis isolates was confirmed by PCR for IS900 and F57 genetic elements. There was a lag time of 2 months after each treatment before M. paratuberculosis was found in leachates. The greatest proportions of M. paratuberculosis-positive leachates were from sandy-soil lysimeters in the manure-treated group receiving the equivalent of 1,000 mm annual rainfall. Under the higher rainfall regimen (2,000 mm/year), M. paratuberculosis was detected more often from lysimeters with loamy soil than sandy soil. Among all lysimeters, M. paratuberculosis was detected more often in grass clippings than in lysimeter leachates. At the end of the trial, lysimeters were disassembled and soil cultured at different depths, and we found that M. paratuberculosis was recovered only from the uppermost levels of the soil columns in the treated group. Factors associated with M. paratuberculosis presence in leachates were soil type and soil pH (P < 0.05). For M. paratuberculosis presence in grass clippings, only manure application showed a significant association (P < 0.05). From these findings we conclude that this pathogen tends to move slowly through soils (faster through sandy soil) and tends to remain on grass and in the upper layers of pasture soil, representing a clear infection hazard for grazing livestock and a potential for the contamination of runoff after heavy rains.

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The concern about accidents involving radioactive materials has led to the search of alternative methods to quickly identify and quantify radionuclides in workers and in the population. One of the options to face up an eventual demand for mass monitoring of internal contamination is the use of a nuclear medicine diagnostic equipment known as gamma camera, a device used to scan patients who have been administered specific amounts of radioactive materials for medical purposes. Although the gamma camera is used for image diagnosis, it can be calibrated with anthropomorphic phantoms or point sources for the quantification of radionuclide activities in the human body. This work presents a protocol for the calibration of gamma cameras for such application. In order to evaluate the suitability of this type of equipment, a gamma camera available in a public hospital located in Rio de Janeiro was calibrated for the in vivo measurement of 131I. The calibration includes the determination of detection efficiencies and minimum detectable activities for each radionuclide. The results show that the gamma camera presents enough sensitivity to detect activity levels corresponding to effective doses below 1 mSv. The protocol is the basis to establish a network of Nuclear Medicine Centres, located in public hospitals in eight countries of Latin America (Argentina, Brazil, Colombia, Cuba, Chile, Mexico, Peru and Uruguay) and in Spain that could be requested to collaborate in remediation actions in the event of an accident involving incorporation of radioactive materials. This protocol is one of the most significant outputs of the IAEA-ARCAL Project (RLA/9/049-LXXVIII) aimed to the Harmonization of Internal Dosimetry Procedures.

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