Catalizzatori polifunzionali per la sintesi di Metil Isobutil Chetone

In this work, we have examined the activity and selectivity of new catalysts for the single-stage production of methyl isobutyl ketone (MIBK, 4- methyl-2-pentanone) from acetone (both in liquid and gas phase), using a fixed bed reactor operated in the temperature range between 373 and 473 K. The main reaction pathways for the synthesis of MIBK from acetone are given in Fig.1. The first step is the self condensation of acetone to diacetone alcohol (DAA, 4-hydroxy-4-methyl-2-pentanone); the second step is the dehydration of DAA to mesityl oxide (MO, 4-methyl-3-penten-2-one); the final step is the selective hydrogenation of the carbon–carbon double bond of MO to form MIBK. The most commonly observed side reactions are over-condensations and unselective hydrogenations (also shown in Fig.1). Two types of catalysts were studied: i)Pd supported on MgO-SiO2 mixed oxides with ratio of Mg to Si, synthetized using Ohnishi’s method and ii)Pd supported on alumina doped with 5% or 10% of MgO. The different Mg-Si and Mg-Al catalysts were characterized by different techniques (XRD, BET, SEM, NH3-TPD and CO2-TPD) and tested under different conditions in the condensation of acetone to diacetone alcohol and its dehydration to mesityl oxide to enhance the activity. Palladium was chosen as metal component, and its hydrogenation activity was studied. A low hydrogenation activity negatively affects the acetone conversion and promotes the production of mesityl oxide. Hydrogenation conditions being too severe may favor the unwanted hydrogenation of acetone to 2-propanol and of MIBK to methyl isobutyl carbinol (MIBC, 4-methyl-2-pentanol) but this effect is less detrimental to the MIBK selectivity than an unsufficient hydrogenation activity.

DNA damage induced by low energy electrons (LEEs)

Abstract : The major objective of our study is to investigate DNA damage induced by soft X-rays (1.5 keV) and low-energy electrons (˂ 30 eV) using a novel irradiation system created by Prof. Sanche’s group. Thin films of double-stranded DNA are deposited on either glass and tantalum substrates and irradiated under standard temperature and pressure surrounded by a N[subscript 2] environment. Base release (cytosine, thymine, adenine and guanine) and base modifications (8-oxo-7,8-dihydro -2’-deoxyguanosine, 5-hydroxymethyl-2’-deoxyuridine, 5-formyl-2’-deoxyuridine, 5,6-dihydrothymidine and 5,6-dihydro-2’-deoxy uridine) are analyzed and quantified by LC-MS/MS. Our results reveal larger damage yields in the sample deposited on tantalum than those on glass. This can be explained by an enhancement of damage due to low-energy electrons, which are emitted from the metal substrate. From a comparison of the yield of products, base release is the major type of damage especially for purine bases, which are 3-fold greater than base modifications. A proposed pathway leading to base release involves the formation of a transient negative ion (TNI) followed by dissociative electron attachment (DEA) at the N-g lycosidic bond. On the other hand, base modification products consist of two major types of chemical modifications, which include thymine methyl oxidation products that likely arises from DEA from the methyl group of thymine, and 5,6-dihydropyrimidine that can involve the initial addition of electrons, H atoms, or hydride ions to the 5,6-pyrimidine double bond.

Identificação dos produtos de oxidação de glicosfingolípidos por espectrometria de massa

O stress oxidativo está associado ao envelhecimento e a inúmeras patologias, nomeadamente a doenças neurodegenerativas e cardiovasculares, e a diversos outros fatores. O stress oxidativo leva à oxidação de importantes biomoléculas como os lípidos e, ao contrário da maior parte dos produtos de oxidação de fosfolípidos e ácidos gordos insaturados (PUFAS), os produtos de oxidação de glicosfingolípidos (GSLs) têm sido escassamente estudados. Os glicosfingolípidos são moléculas muito diversificadas estruturalmente e com importantes funções, essencialmente no sistema nervoso central (SNC) onde estão localizados maioritariamente. Deste modo, alterações na estrutura dos GSLs conduzirão a consequente comprometimento das suas funções e ao possível desenvolvimento de patologias. Assim para identificar as modificações oxidativas que ocorrem em glicosfingolípidos e pressupor consequentes efeitos biológicos nas células sob stress oxidativo, prepararamse sistemas modelo biomiméticos com diferentes GSLs os quais foram expostos a radicais hidroxilo gerados sob condições da reação de Fenton (H2O2 e Fe2+) e as reações foram monitorizadas por diferentes metodologia utilizando a espectrometria de massa. Os resultados obtidos com este estudo permitiram-nos identificar vários produtos de oxidação produzidos durante a oxidação desta classe de lípidos. Os produtos de oxidação observados em comum, em todos os GSLs estudados (C16:0GalCer, C24:1GalCer, C24:1LacCer e GM1) foram as suas correspondentes ceramidas. Estas atuam como agentes pro-apoptóticos e podem in vivo promover a neurodegeneração nas células sob stress oxidativo. Também foi possível observar produtos com inserção de oxigénio junto às duplas ligações ou na cadeia de esfingosina (no caso do GM1) ou na cadeia de ácido gordo monoinsaturada (no caso da C24:1GalCer, C24:1LacCer), corroborando o facto de que ácidos gordos saturados não são susceptíveis à oxidação por radicais. Interessantemente em ambos os GSLs de cadeias glicosiladas compostas com mais de um açúcar (C24:1LacCer e GM1) observou-se a despolimerização oxidativa da porção glicosilada por quebra das correspondentes ligações glicosídicas. Esta degradação leva à formação de GlcCer no caso de oxidação de LacCer ou na formação de outros gangliósidos (GM2, GM3, asialoGM1 e asialoGM2) e glicolípidos (LacCer e GlcCer), no caso de oxidação de GM1. A formação por via radicalar não enzimática destes GSLs leva a distúrbios no perfil lipídico. Previamente, em certas doenças, foram observadas variações na concentração do perfil de gangliósidos e de ceramidas. Estes dados permitem sugerir que em células em condições de stress oxidativo, a acumulação de gangliósidos mais simples e ceramidas poderá ter uma contribuição de produtos da degradação oxidativa dos gangliósidos e GSLs mais complexos. Este trabalho contribui assim para uma melhor compreensão das modificações estruturais que ocorrem em alguns glicosfingolípidos em condições de stress oxidativo. Os produtos de oxidação aqui identificados suportam a sua possível futura deteção em sistemas biológicos.

Analyse des signaux radars polarimétriques en bandes C et L pour le suivi de l'humidité du sol de sites forestiers

Résumé : Dans les couverts forestiers, le suivi de l’humidité du sol permet de prévenir plusieurs désastres tels que la paludification, les incendies et les inondations. Comme ce paramètre est très dynamique dans l’espace et dans le temps, son estimation à grande échelle présente un grand défi, d’où le recours à la télédétection radar. Le capteur radar à synthèse d’ouverture (RSO) est couramment utilisé grâce à sa vaste couverture et sa résolution spatiale élevée. Contrairement aux sols nus et aux zones agricoles, le suivi de l’humidité du sol en zone forestière est très peu étudié à cause de la complexité des processus de diffusion dans ce type de milieu. En effet, la forte atténuation de la contribution du sol par la végétation et la forte contribution de volume issue de la végétation réduisent énormément la sensibilité du signal radar à l’humidité du sol. Des études portées sur des couverts forestiers ont montré que le signal radar en bande C provient principalement de la couche supérieure et sature vite avec la densité de la végétation. Cependant, très peu d’études ont exploré le potentiel des paramètres polarimétriques, dérivés d’un capteur polarimétrique comme RADARSAT-2, pour suivre l’humidité du sol sur les couverts forestiers. L’effet du couvert végétal est moins important avec la bande L en raison de son importante profondeur de pénétration qui permet de mieux informer sur l’humidité du sol. L’objectif principal de ce projet est de suivre l’humidité du sol à partir de données radar entièrement polarimétriques en bandes C et L sur des sites forestiers. Les données utilisées sont celles de la campagne terrain Soil Moisture Active Passive Validation EXperiment 2012 (SMAPVEX12) tenue du 6 juin au 17 juillet 2012 au Manitoba (Canada). Quatre sites forestiers de feuillus ont été échantillonnés. L’espèce majoritaire présente est le peuplier faux-tremble. Les données utilisées incluent des mesures de l’humidité du sol, de la rugosité de surface du sol, des caractéristiques des sites forestiers (arbres, sous-bois, litières…) et des données radar entièrement polarimétriques aéroportées et satellitaires acquises respectivement, en bande L (UAVSAR) à 30˚ et 40˚ et en bande C (RADARSAT-2) entre 20˚ et 30˚. Plusieurs paramètres polarimétriques ont été dérivés des données UAVSAR et RADARSAT-2 : les coefficients de corrélation (ρHHVV, φHHVV, etc); la hauteur du socle; l’entropie (H), l’anisotropie (A) et l’angle alpha extraits de la décomposition de Cloude-Pottier; les puissances de diffusion de surface (Ps), de double bond (Pd) extraites de la décomposition de Freeman-Durden, etc. Des relations entre les données radar (coefficients de rétrodiffusion multifréquences et multipolarisations (linéaires et circulaires) et les paramètres polarimétriques) et l’humidité du sol ont été développées et analysées. Les résultats ont montré que 1) En bande L, plusieurs paramètres optimaux permettent le suivi de l’humidité du sol en zone forestière avec un coefficient de corrélation significatif (p-value < 0,05): σ[indice supérieur 0] linéaire et σ[indice supérieur 0] circulaire (le coefficient de corrélation, r, varie entre 0,60 et 0,96), Ps (r entre 0,59 et 0,84), Pd (r entre 0,6 et 0,82), ρHHHV_30˚, ρVVHV_30˚, φHHHV_30˚ and φHHVV_30˚ (r entre 0,56 et 0,81) alors qu’en bande C, ils sont réduits à φHHHV, φVVHV et φHHVV (r est autour de 0,90). 2) En bande L, les paramètres polarimétriques n’ont pas montré de valeur ajoutée par rapport aux signaux conventionnels multipolarisés d’amplitude, pour le suivi de l’humidité du sol sur les sites forestiers. En revanche, en bande C, certains paramètres polarimétriques ont montré de meilleures relations significatives avec l’humidité du sol que les signaux conventionnels multipolarisés d’amplitude.

Direct synthesis of β-ketophosphonates and vinyl phosphonates from alkenes or alkynes catalyzed by CuNPs/ZnO

Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be dependent on the nature of the alkyne. Thus, alkynes conjugated with an aromatic ring or a carbon–carbon double bond gave β-ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group led to the formation of the corresponding vinyl phosphonates.

Bond characteristics between CFRP and steel plates in double strap joints

This paper describes a series of double strap shear tests loaded in tension to investigate the bond between CFRP sheets and steel plates. Both normal modulus (240 GPa) and high modulus (640 GPa) CFRPs were used in the test program. Strain gauges were mounted to capture the strain distribution along the CFRP length. Different failure modes were observed for joints with normal modulus CFRP and those with high modulus CFRP. The strain distribution along the CFRP length was found to be similar for the two cases. A shorter effective bond length was obtained for joints with high modulus CFRP whereas larger ultimate load carrying capacity can be achieved for joints with normal modulus CFRP when the bond length is long enough. The Hart-Smith Model was modified to predict the effective bond length and ultimate load carrying capacity of joints between the normal modulus CFRP and steel plates. The Multilayer Distribution Model developed by the authors was modified to predict the load carrying capacity of joints between the high modulus CFRP and steel plates. The predicted values agreed well with experimental ones.

Double strap joint tests to determine the bond characteristics between CFRP and steel plates

Advanced composite materials offer remarkable potential in the upgrade of civil engineering structures. The evolution of CFRP (carbon fibre reinforced polymer) technologies and their versatility for applications in civil constructions require comprehensive and reliable codes of practice. Guidelines are available on the rehabilitation and retrofit of concrete structures with advanced composite materials. However, there is a need to develop appropriate design guidelines for CFRP strengthened steel structures. It is important to understand the bond characteristics between CFRP and steel plates. This paper describes a series of double strap shear tests loaded in tension to investigate the bond between CFRP sheets and steel plates. Both normal modulus (240 GPa) and high modulus (640 GPa) CFRPs were used in the test program. Strain gauges were mounted to capture the strain distribution along the CFRP length. Different failure modes were observed for joints with normal modulus CFRP and those with high modulus CFRP. The strain distribution along the CFRP length is similar for the two cases. A shorter effective bond length was obtained for joints with high modulus CFRP whereas larger ultimate load carrying capacity can be achieved for joints with normal modulus CFRP when the bond length is long enough.

Preliminary bond-slip model for CFRP sheets bonded to steel plates

Carbon fiber reinforced polymer (CFRP) sheets have established a strong position as an effective method for innovative structural rehabilitation. However, the use of externally bonded CFRP in the repair and rehabilitation of steel structures is a relatively new technique that has the potential to improve the way structures are repaired. An important step toward understanding bond behaviour is to have an estimation of local bond stress versus slip relationship. The current study aims to establish the bond-slip model for CFRP sheets bonded to steel plate. To obtain the shear stress versus slippage relationship, a series of double strap tension type bond tests were conducted. This paper reports on the findings of the experimental studies. The strain and stress distributions measured in the specimens for two different bond lengths. The results show a preliminary bi-linear bond-slip model may be adopted for CFRP sheet bonded with steel plate.

Reversible double insertion of aryl isocyanates into the Ti-O bond of titanium(IV) isopropoxide

The insertion of phenyl isocyanate into titanium isopropoxide leads to the formation of a dimeric complex [Ti(O ' Pr)(2)(mu-O ' Pr){C6H5N(O ' Pr)CO}](2) (1) which has been structurally characterized. Reaction of titanium isopropoxide with two and more than 2 equiv. of phenyl isocyanate is complicated by competitive, reversible insertion between the titanium carbamate and titanium isopropoxide. The ligand formed by insertion of phenyl isocyanate into the titanium carbamate has been structurally characterized in its protonated form C6H5N{C(O ' Pr)O}C(O)N(H)C6H5 (3aH). Insertion into the carbamate is kinetically favored whereas insertion into isopropoxide gives the thermodynamically favored product. (c) 2004 Elsevier B.V. All rights reserved.

Structure-specific nuclease activity of RAGs is modulated by sequence, length and phase position of flanking double-stranded DNA

RAGs (recombination activating genes) are responsible for the generation of antigen receptor diversity through the process of combinatorial joining of different V (variable), D (diversity) and J (joining) gene segments. In addition to its physiological property, wherein RAG functions as a sequence-specific nuclease, it can also act as a structure-specific nuclease leading to genomic instability and cancer. In the present study, we investigate the factors that regulate RAG cleavage on non-B DNA structures. We find that RAG binding and cleavage on heteroduplex DNA is dependent on the length of the double-stranded flanking region. Besides, the immediate flanking double-stranded region regulates RAG activity in a sequence-dependent manner. Interestingly, the cleavage efficiency of RAGs at the heteroduplex region is influenced by the phasing of DNA. Thus, our results suggest that sequence, length and phase positions of the DNA can affect the efficiency of RAG cleavage when it acts as a structure-specific nuclease. These findings provide novel insights on the regulation of the pathological functions of RAGs.

Double cyclometalation via carbon-silicon bond cleavage by palladium(II) acetate. X-ray structure of a cationic 1,4-dipalladated benzene ring and selective synthesis of heterobimetallic 1,4-phenylene-bridged platinum(II)-palladium(II) complexes

The disilylated compound 1,4-bis(trimethylsilyl)-2,3,5,6-tetrakis((dimethylamino)methyl)benzene, (Me(3)Si)(2)C2N4, 4, can be electrophilically palladated selectively at the C-Si bonds to afford the neutral 1,4-bis(palladium) complex [(AcOPd)(2)(C2N4)], from which the dicationic [(LPd)(2)(C2N4)](2+) (L = MeCN) organometallic species are accessible. The monosilylated species (Me(3)Si)(H)C2N4, 5, can be used for the preparation of the dicationic heterodinuclear platinum(II)-palladium(II) species [(LPd)(LPt)(C2N4)](2+) (L = MeCN) via a sequence of transmetalation of the organolithium derivative of 5 with [PtCl2(SEt(2))(2)], followed by a C-Si bond palladation reaction.

Effect of an ancillary ligand on single helix-double helix interconversion in copper complexes. Copper(I)-water bond

Reaction of Cu(ClO(4))(2)center dot 6H(2)O with the 1:2 condensate of benzildihydrazone and 2-acetylpyridine, in methanol in equimolar ratio yields a green compound which upon recrystallisation from 1:1 CH(2)Cl(2)-C(6)H(6) mixture affords [CuL(H(2)O)](ClO(4))(2)center dot 1/2C(6)H(6). The complex crystallises in the space group P-1 with a = 8.028(11) angstrom, b = 12.316(17) angstrom, c = 18.14(3) angstrom, alpha = 97.191(10)degrees, beta = 94.657(10)degrees and gamma = 108.039(10)degrees. It is single helical with the metal having a distorted trigonal bipyramidal N(4)O coordination sphere. The acid dissociation constant of the Cu(I) complex in CH(3)CN is 3.34 +/- 0.19. The X band EPR spectrum of the compound is rhombic with g(1) = 2.43, g(2) = 2.10 g(3) = 2.02 and A(1) = 79.3 x 10(-4) cm(-1). The Cu(II/I) potential of the complex in CH(2)Cl(2) at a glassy carbon electrode is 0.43 V vs SCE. It is argued that the copper-water bond persists in the corresponding copper(I) species. Its implications on the single helix-double helix interconversion in copper helicates are discussed. DFT calculations at the B3LYP/6-311G** level shows that the binding energy of water in the single helicol live-coordinate copper(I) species [CuL(H(2)O)](+) is similar to 40 kJ mol(-1).