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121.
122.
Helio G. Bonacorso Cleber A. Cechinel Jussara Navarini Rosália Andrighetto Marcos A. P. Martins Nilo Zanatta 《Monatshefte für Chemie / Chemical Monthly》2011,21(6):277-285
Abstract
This work describes the regioselective synthesis of two new series of 1,1′-oxalylbis[3-(alkyl/aryl/heteroaryl)-4,5-dihydro-5-hydroxy-5-(trihalomethyl)-1H-pyrazoles], where the 3-substituents are H, Me, C6H5, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-NO2C6H4, 4,4′-BiPh, and 2-furyl, in a one-pot methodology with ethanol as solvent, from the reaction of 4-alkoxy-4-(alkyl/aryl/heteroaryl)-1,1,1-trihaloalk-3-en-2-ones with oxalyldihydrazide (51–89%). Complementarily, the dehydration reactions of five examples of the described oxalylbispyrazolines are also reported, which furnished the respective 1,1′-oxalylbis[3-(alkyl/aryl/heteroaryl)-5-(trihalomethyl)-1H-pyrazoles] in 53–78% yields without the two C(O)–N bond cleavages. 相似文献123.
Transport behavior of humic acid-modified nano-hydroxyapatite in saturated packed column: effects of Cu, ionic strength, and ionic composition 总被引:1,自引:0,他引:1
Wang D Chu L Paradelo M Peijnenburg WJ Wang Y Zhou D 《Journal of colloid and interface science》2011,360(2):398-407
The surfaces of nano-hydroxyapatite (nHAP) used for contaminated soil and groundwater remediation may be modified to render nHAP highly mobile in the subsurface. Humic acid (HA) is widely used to modify and stabilize colloid suspensions. In this work, column experiments were conducted to determine the effects of contaminant (e.g., Cu) concentration, ionic strength (IS), and ion composition (IC) on the transport behavior of HA-modified nHAP in saturated packed columns. IS and nature of the cation had strong effects on the deposition of nHAP, and the effect was greater for divalent than for monovalent cations. Divalent cations have a greater capacity to screen the surface charge of nHAP, and Ca(2+) bridges the HA-modified nHAP colloidal particles, which causes greater deposition. Moreover, Cu(2+) had a greater effect on the transport behavior than Ca(2+) due to their strong exchange with Ca(2+) of nHAP and its surface complexation with nHAP. The relative travel distance L(T), of the injected HA-modified nHAP colloids, ranges from less than one to several meters at varying Cu concentrations, ISs, and ICs in saturated packed columns. The results are crucial to evaluate the efficacy of nHAP on the remediation of contaminated soil and groundwater environments. 相似文献
124.
Iglesias-Juez A Kubacka A Fernández-García M Di Michiel M Newton MA 《Journal of the American Chemical Society》2011,133(12):4484-4489
A combination of time-resolved X-ray absorption spectroscopy (XAS), hard X-ray diffraction (HXRD), diffuse reflectance infrared spectroscopy (DRIFTS), and mass spectrometry (MS) reveals a series of size-dependent phenomena at Pd nanoparticles upon CO/(NO+O(2)) cycling conditions. The multitechnique approach and analysis show that such size-dependent phenomena are critical for understanding Pd CO elimination behavior and, particularly, that different Pd(I) and Pd(0) centers act as active species for a size estimated by XAS to be, respectively, below and above ca. 3 nm. The relative catalytic performance of these two noble metal species indicates the intrinsic higher activity of the Pd(I) species. 相似文献
125.
Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry 总被引:1,自引:0,他引:1
It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25 J cm−2). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 μs, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 μm. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity. 相似文献
126.
Núria Mas Alessandro Agostini Dr. Laura Mondragón Dr. Andrea Bernardos Dr. Félix Sancenón Dr. M. Dolores Marcos Prof. Ramón Martínez‐Máñez Prof. Ana M. Costero Prof. Salvador Gil Prof. Matilde Merino‐Sanjuán Prof. Pedro Amorós Dr. Mar Orzáez Prof. Enrique Pérez‐Payá 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1346-1356
The preparation of a new capped silica mesoporous material, Rh‐Azo‐S , for on‐command delivery applications in the presence of target enzymes is described. The material consists of nanometric mesoporous MCM‐41‐like supports loaded with Rhodamine B and capped with an azopyridine derivative. The material was designed to show “zero delivery” and to display a cargo release in the presence of reductases and esterases, which are usually present in the colon, mainly due to intestinal microflora. The opening and cargo release of Rh‐Azo‐S in vitro studies were assessed and seen to occur in the presence of these enzymes, whereas no delivery was noted in the presence of pepsine. Moreover, Rh‐Azo‐S nanoparticles were used to study controlled Rhodamine B dye delivery in intracellular media. HeLa cells were employed for testing the “non”‐toxicity of nanoparticles. Moreover, delivery of the dye in these cells, through internalization and enzyme‐mediated gate opening, was confirmed by confocal microscopy. Furthermore, the nanoparticles capped with the Azo group and loaded with a cytotoxic camptothecin ( CPT ) were also prepared (solid CPT‐Azo‐S ) and used as delivery nanodevices in HeLa cells. When this solid was employed, the cell viability decreased significantly due to internalization of the nanoparticles and delivery of the cytotoxic agent. 相似文献
127.
Dr. Ángel J. Jiménez Michael Sekita Dr. Esmeralda Caballero Dr. M. Luisa Marcos Dr. M. Salomé Rodríguez‐Morgade Prof. Dr. Dirk M. Guldi Prof. Tomás Torres 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14506-14514
In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of PtII disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of PtII between Pc and PDI impacts the results in a longer‐lived Pc . +/PDI . ? radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 . 相似文献
128.
129.
Helio Gauze Bonacorso Arci Dirceu Wastowski Nilo Zanatta Marcos Antonio Pinto Martins 《合成通讯》2013,43(8):1457-1465
A convenient method for the synthesis of alkyl[aryl]-substituted 5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-methylpyrazole (2) from a new ring transformation reaction of alkyl[aryl]-substituted-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-pyrazolethiocarboxyamide (1) with methylhydrazine in THF, and the thermal dehydration of 2, are reported. 相似文献
130.
Silvia Hernández-Ainsa Rafael Alcalá Joaquín Barberá Mercedes Marcos Carlos Sánchez José Luis Serrano 《European Polymer Journal》2011,(3):311-318
A series of codendrimers has been prepared by the grafting of poly(propylene imine) PPI-(NH2)16 (G = 3) with two different carboxylic acids: the aromatic-based 5-[4′-(4-cyanophenylazo)phenyloxy]pentanoic acid (AZO) and the aliphatic 2,2-bis(undecanoyloxymethylene)propionic acid (BUPA) in different proportions. Their thermal properties, liquid crystalline behavior and photoinduced optical anisotropy have been investigated. The formation of the ionic compounds was confirmed by nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. The influence of the acid percentage in the liquid crystalline behavior was investigated by means of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffractometry (XRD). All the resulting co-dendrimers present liquid crystalline properties displaying an evolution from nematic mesophase for the azo-richer dendrimers to smectic A mesophase for the BUPA-richer dendrimers. Only materials with low azobenzene contents up to four AZO units per dendrimer on average were processable by casting from dichloromethane solutions and resulted in transparent thin films appropriate for optical studies. The photoinduced dichroism reached was higher in the dendrimer with higher azo content (four units per dendrimer) being this material a good compromise between processability and optical response. 相似文献