A. F. A. Marques

Ruthenium organometallic compounds as promising anti-metastatic drugs for breast cancer chemotherapy

W demonstrate for the first time the fabrication of ultrathin palladium membrane on porous nickel rod type support with mechanical treatment for H2 separation. Porous nickel membrane has so small and uniform pore size to be the support of dense Pd membrane. However, small nickel cluster on surface caused defects on Pd membrane supported by porous Ni rod because porous Ni rod is made by uniaxial pressing. The effect of mechanical treatment was found to have a significant effect on surface to get rid of small nickel cluster as well as selectivity to reduce pore size. After 10 cycles electroless plating, as-deposited Pd film is uniform and defect-free except few pinholes. Pinholes were eliminated through 100 nmthick Pd thin film deposited by the DC magnetron sputtering process. The gas permeation properties of Pd membranes were characterized by permeation experiments with H2, N2, CO, and CO2 single gases at 623K with a pressure of 1~4 bar. Also, gas permeation properties of Pd membranes were characterized by permeation experiments with mixture gas (N2:CO2:H2:CO:H2O = 0.275:0.129:0.235:0.002:0.359 mole fraction) at 623 K with a pressure of 1~4 bar. It was clarified that the surface condition of porous nickel rod is very important to the H2 permeability and selectivity because the permeation of H2 gas was contributed by solution diffusion mechanis. And to conclude, Pd membranes on porous Ni support in this study showed superior performances, and proved to be impermeable to carbon monoxide.T properties of plant are attributed to bioactive compounds found within them. These compounds can be promising candidates for drug development. This presentation focused on the wound healing and anti-inflammatory properties of Hemigraphis alternata and that the isolation and identification using chromatography and spectroscopic methods is currently employed. Available treatments for wound healing and inflammation are antibiotics and anti-inflammatory drugs, which some are reported to be high cost, low availability and associated with adverse effects. Therefore there is a need to search for alternatives treatments and plant-based drugs represent a key prospect to it. The leaves of Hemigraphis alternata exhibited promising wound healing and anti-inflammatory activities through scratch assay, tube formation assay, nitric oxide production inhibition assay, cytokine TNF-α production inhibition assay and lipoxygenase enzyme inhibition assay. To the best of our knowledge, this is the first report on the bioactivities of Hemigraphis alternata.R complexes are the most widely studied non-platinum metallodrugs and hold great potential as alternatives in cancer therapy. During the recent years our group has been putting a significant effort on the synthesis of new half sandwich “Ru(η-C5H5)” derived compounds which cytotoxicity was found, in most of the cases, better than that of cisplatin against several cancer cell lines of typically low, medium and high resistance to metallodrugs. Our studies in vivo involving triple negative breast cancer (TNBC) tumors showed that our Lead compound had the dual capacity to inhibit the development of metastasis and to suppress significantly the tumour growth. We will report here our progressing studies concerning our Lead drug, such as uptake and cell death mechanisms, modulation, biodistribution, blood speciation, just to give some examples, considered crucial to the progression of our drug into clinical evaluation. Our gathered results indicate so far the relevance of this new family of half sandwich compounds as potential anticancer agents with particular importance for TNBC for which there is not available in clinic any efficient chemotherapeutic agent.The proteasome core particle (CP) has the substrate translocation channel that is topologically blocked by the N-termini of the alpha subunits when it is in the closed form. For substrate degradation, the gate of CP channels is opened upon association with the regulatory particle (RP) or other proteasome activators. Here we show that deletion of the N-terminal tails of the alpha3 subunits (alpha3deltaN) constitutively opens the CP gate of mammalian proteasomes without affecting their structural integrity. The hyperactivity of open-gated alpha3deltaN proteasomes was observed both in 20S and 26S measured by small fluorogenic peptide substrates and polyubiquitinated Sic1 (Ub-Sic1). The cells, which express alpha3deltaN proteasomes showed significantly facilitated degradation of various proteasome substrates. Delayed aggregation formation of tau proteins, and promoted cell survival against oxidative stress. These data demonstrate that the regulation of CP gate function as a ratelimiting step of proteasomal degradation and opening the CP gate may be an effective strategy to increase proteasome activity and to reduce levels of aberrantly overexpressed proteins in cells.T caffeic acid-derived polyether poly[3-(3,4-dihydroxyphenyl)glyceric acid] (PDPGA) isolated from comfrey species is a biologically active, water soluble polymer with antioxidant, antilipoperoxidant, antiinflammatory and anticancer properties. This compound is a representative of a new class of natural polyethers The first step for obtaining of PDPGA analogue was performed by cationic polymerization of 2-methoxycarbonyl-3-(3,4-dimethoxyphenyl)-oxirane (MCDMPO). An unsymmetrically 2,3-disubstituted oxirane monomer was synthesized from veratraldehyde (3,4-dimethoxybenzaldehyde, methyl vanillin) and methyl chloroacetate. MCDMPO was polymerized using BF3·OEt2 in CH2Cl2 under various conditions. Under all conditions examined, the monomer was almost completely consumed to afford a polymer. Mn of the polymer ranged from 2900 to 12 800 as determined by size-exclusion chromatography (SEC) with right-angle laser light scattering detection. MCDMPO leads to a polymer having a rather stiff conformation having a novel π-stacked structure between aromatic and carbonyl groups of neighbouring monomeric units, leading to ICT interactions. Although regulated π-stacked structures of a polymer have been prepared for accumulated aromatic groups in the sideand main-chain, such a “hetero π-stacked conformation” of the polymer chain consisting of different types of π-electron systems is unprecedented to the best of our knowledge.D salts are used in organic synthesis as versatile arylating agents and for other many applications. However, the methods utilizing these salts in synthesis still have limitations, such as the requirements of base, and sometimes accompanied problems in the product yields and aryl selectivities for low nucleophilic compounds and the salts having two different aryl groups. Herein, we have developed a more efficient arylation of carboxylic acids meeting green chemistry by utilizing new conceptual diaryliodonium salts. By utilizing the newly designed salts 1, the efficient metal-free arylations of carboxylic acids occur upon heating without base and solvent, giving aryl esters in extremely high yields in short reaction times. In comparison, the reactions are more efficient, especially for low nucleophilic carboxylic acids, such as p-nitrobenzoic acid, that were unsatisfactory as substrates in known intermolecular coupling methods using ordinary diaryliodonium salts. In addition, the arylations usually proceeded with perfect chemoselectivities even in the presence of other nucleophilic groups.E and selective syntheses of nitrogen-containing heterocycles have attracted considerable attention from many chemists due to their particular interest within the realm of organic and medicinal chemistry. Recent advances in the field of ring-expansion chemistry, involving 1-azoniabicyclo[n.1.0]alkane scaffolds (bicyclic aziridinium ions) as a key transient intermediates, made it possible to efficiently construct a broad variety of mediumand large-sized functionalized nitrogencontaining heterocycles. The deployment of 2-(3-hydroxypropyl)aziridine for the synthesis of a variety of 3-substituted piperidines and their regioisomeric pyrrolidines has extensively been investigated. The structure of the decisive 1-azoniabicyclo [3.1.0] hexane tosylate was identified by means of NMR analysis, which was treated with various nucleophiles in CH3CN. The ring-opening reactions proceed through two different pathways to yield either pyrrolidines or piperidines, depending on the nature of the selected nucleophile. These regioselective nucleophile-dependent ring transformations were also supported by DFT-calculations to rationalize the observed reactivities. In the same manner 1-azoniabicyclo [4.1.0] hepane tosylate was prepared and its ring opening was also achieved by various nucleophiles. The regiochemical pathways of its ring opening are quite similar to the previous case in 1-azoniabicyclo [3.1.0] hexane tosylate depending on the nature of nucleophile to afford either piperidine and (or) azepane as the kinetic and the thermodynamic products respectively.I of functional solid materials is an important topic in the field of chemistry and materials science. Our laboratory has paid attention to cyanido-bridged metal assemblies and nano-sized metal oxide systems. Cyanido-bridged assemblies are suitable systems to control electronic and magnetic state by external stimuli and observed humidity sensitive magnetism, interference effect between magnetic ordering and ionic conductivity, photo-induced magnetization due to charge transfer induced spin transition and spin-crossover phenomenon, and nonlinear magneto-optical effect, chiral photo-switching magnet exhibiting orthogonal switching of polarization of second harmonic light by photo-irradation, etc. Furthermore, by utilizing nano-scale chemical synthesis, we have realized huge coercive field, electromagnetic wave absorption, room temperature photo-induced phase transition, and thermal energy storage in nano-sized metal oxides from abundant elements such as iron or titanium. In this presentation, I will introduce syntheses, functionalities, and mechanisms of some of these functional cyanido-bridged metal assemblies and metal oxide nano materials based on rational design and strategies.Ammonia concentration may increase or decrease due to the mishandling of blood specimens. Among the factors that affect ammonia concentration ,blood collection, type of anticoagulant, promptness of centrifugation ,temperature and complete fillin g of blood collection tube. The use of non -hemolysed , non-clotted specimen and prompt centrifugation (1500 X g ; 15 minutes ) apparently were important in avoiding such increase in ammonia concentration. Sodium citrated -plasma is preferred over the other anti-coagulated specimens for ammonia determination . Complete filling of the specimen tube has no significant effect on ammonia concentration. We concluded that the procedure for collection and handling of specimen for ammonia determination should be standardized and strictly observed .

Mixed Adenoneuroendocrine Carcinoma Causing Colonic Intussusception

Colonic intussusception is a rare cause of intestinal obstruction in adults and is caused by a malignant lesion in about 70% of cases. Early diagnosis and treatment are essential. We present a 64-year-old male patient with right colonic intussusception caused by a mixed adenoneuroendocrine carcinoma (MANEC), presenting as a giant pedunculated polyp (54 mm of largest diameter). The patient underwent right colectomy with primary anastomosis and adjuvant chemotherapy. The diagnosis of intussusception of the colon in adults is difficult because of its rarity and nonspecific clinical presentation. In this case, the cause was a rare histological type malignant tumor (MANEC).

Azores sea: Seafloor hydrothermal systems, VMS deposits and new exploration targets

The Mid-Atlantic Ridge (MAR), south of the Azores islands, hosts active seafloor hydrothermal systems both in enriched basalts (Menez Gwen, Lucky Strike) and serpentinized peridotites (Rainbow). These Cu and Zn-rich hydrothermal systems inherited their particular geochemistry from their host rocks that, in turn, is influenced by the Azores plume. The Terceira Rift (TR) in the Azores is an ultraslow spreading ridge with active volcanism, melting anomalies and permanent tectonic activity making it a promising and potential target for the exploration of seafloor hydrothermal systems, capable of forming massive sulfide deposits.