Synthesis and characterization of large surface hexagonal polyoxometalate platelets

The polyoxometalates, or POMs (clusters comprising at least two metal and many oxygen atoms), have recently gained significant interest, owing to their versatile architecture and especially catalytic activities. Due to their high catalytic activity but low surface area, there is always a demand for making high-surface-area POMs, particularly high-surface-area Keggins. Our present work demonstrates the 'gluing' of the anionic phosphomolybdate Keggin on gibbsite nanoplatelets with a residual positive charge to form large-surface-area composites. The resulting composite reported here has been characterized using TEM imaging, EDX/TEM (elemental) analysis, FTIR spectroscopy, potentiometric titrations, electrophoretic mobility determination, and XRD. The composite reported here could be useful in catalysis.     

Trends in CE-MS 2005-2006

CE-MS has gained further attention as a multidimensional analytical approach. The number of publications dealing with this technique is still increasing on the level of application as well as method development-oriented approaches. Additionally, 15 reviews were published the last two years focusing on CE-MS. An overview of all papers found to have been published within 2005 and 2006 is given in tabulated form. Additionally, four promising technical trends are chosen to be presented in detail: (i) chip-based CE-MS, (ii) capillary coatings in CE-MS, (iii) new trends in CEC-MS and (iv) the application of 2-D CE-MS.     

Dicyanomethylene compounds and heterocyclization of acylthiosemicarbazides

(1,3‐Dioxo‐2,3‐dihydro‐1H‐inden‐2‐ylidene)propanedinitrile ( 1 , in ethyl acetate solution), 3‐(dicyano‐methylene)‐2‐indolone ( 2 , in ethanol/piperidine solution) and 7,7′,8,8′‐tetracyanoquinodimethane ( 3 , in pyridine solution) act on substituted acylthiosemicarbazides 4a‐d , forming the derivatives of oxoindeno‐pyrrolylidenehydrazide ( 5a‐d and 7a‐d ), thiazoloindolylidenehydrazide ( 12a‐d ), pyrroloindolylidene‐hydrazide ( 13a‐d ) and spiro[pyrrolylidene‐4,1′(cyclohexa‐2′,5′‐dienylidene)]propanedinitrile ( 18a‐d ). Rationales for these conversiones involving the nucleophilic addition on dicyanomethylene carbon atom are presented.     

Synthesis, characterization and photophysical properties of benzidine-based compounds

The N-alkylation of the 3,3′-diaminobenzidine with innocent substituents leads to unusual properties. The emission of the benzidine core can be fine-tuned by subtle modifications, and the N-substitution with benzylic groups results in photoinduced exciplexes with distinct and increased emission. This compound constitutes the first example of intramolecular exciplex containing benzidine unit. We also show that these photoinduced processes could be modulated by proton input, and that the diprotonation of the benzidine core disrupted the intramolecular communication in the excited states with a concomitant inhibition of the ligand-centred fluorescence. Furthermore, upon photo-irradiation at 254 nm, semiquinone imine and quinone diimine systems are produced in CH₂Cl₂ of which the photolysis generates Cl radicals, which rapidly oxidize the tetraamine compounds.     

Hybrid of the 1,2,3-triazole nucleus and sesquiterpene skeleton as a potential antitumor agent: Hemisynthesis,molecular structure,Hirshfeld surface analysis,density functional theory,and in vitro cytotoxic and apoptotic effects

A new 1,2,3-triazole sesquiterpenic named (4aR,5aS,7aR,10aR,10bR)-10-benzyl-5,5-dichloro-1,1,4a,7a-tetramethyl-1,2,3,4,4a,5,7a,10,10a,10b decahydrocyclopropa[2′,3′]cyclohepta [1′,2′:3,4]benzo[1,2-d][1,2,3]triazol-7(6H)-one was synthesized by a dipolar cycloaddition 1,3 between benzyl azide and α,β-unsaturated sesquiterpene ketone catalyzed by titanium tetrachloride TiCl₄. It was obtained with a good yield and characterized using single-crystal X-ray diffraction technique, infra red (IR) spectroscopy, High Resolution Mass Spectrometry (HRMS), UV-Visible, and ¹H and ¹³C NMR spectroscopies. The optimization by the density functional theory (DFT) method was carried out to study the formation mechanism of the derivative. The selected compounds 1 – 4 exhibited anticancer activities in vitro against namely fibrosarcoma (HT-1080), lung carcinoma (A-549), and breast (MCF-7 and MDA-MB-231 cell lines with IC₅₀ in the range of 10.02–44.71 μM). In addition to using flow cytometry and the apoptosis assay, cell cycle arrest at the S phase (10 μM) and G2/M arrest in (5 and 10 μM) was performed for compound 4 in fibrosarcoma (HT-1080) cancer cells. Results suggested that compound 4 test with good activity against HT-1080 cells with IC₅₀ value from 10.02 μM and induced the apoptotic effect. Theoretical studies were realized to estimate the molecular proprieties that lead to a high potential of cytotoxic effect, which is in agreement with the experimental results.     

Comparison of theoretical and measured P1dB of a photonic microwave link: influence of some physical parameters of the DFB laser

This paper studies a microwave photonic link built as an IM/DD or intensity modulation–direct detection semiconductor laser system. The radiofrequency gain and 1 dB compression point of the link are both simulated with a modelling approach and compared to measurements. The electrical model of the electro-optic transducer, a distributed feedback laser, is first presented. Taking into account the nonlinearities and noise sources, it is developed on the commercial electrical software Advanced Design System. Owing to this accurate model, the impact of the relaxation oscillation frequency is presented on the system nonlinearity characteristic as for example the input 1 dB compression point. The comparison of simulated results to measured ones confirms the accuracy of this model.     

A low cost implementation of the Phillips model in solid–liquid flow modeling

The interpolation requirements for the loosely coupled finite element solution of the Navier–Stokes equations and Phillips shear‐induced particle diffusion model are discussed. It is shown that a second‐order approximation of the fluid velocity field is required to adequately capture the spatial derivatives of the rate‐of‐strain tensor. To circumvent this limitation, a shear‐rate smoothing procedure is introduced, thereby allowing the use of lower‐order approximations for the fluid phase. Numerical experiments comparing the convergence and CPU cost of the different tetrahedral interpolation bases are presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrical characterization and modeling of Au/MEH-PPV/porous n+-GaAs/n+-GaAs heterojunction in direct and alternating current mode

Assembled heterojunction was fabricated by spin-coating poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene-vinylene)] (MEH-PPV) thin layers on straight and porous n⁺-GaAs substrates. The current–voltage and capacitance–voltage studies have shown an abrupt junction behavior with current conduction governed by SCLC and thermionic modes. Andersons' rules were used to determine depletion width and balance bands discontinuities for both heterojunctions. Capacitance and conductance vs. frequency techniques were used to evaluate the density of interface states. Density values obtained from both techniques were in a good agreement.     

The effect of thiourea as a complexing agent on the separation of metallic ions through cation exchange membranes by Donnan dialysis

Donnan dialysis has been investigated in this work in the order to exhibit the influence of the composition of solution on the performance of commercial cation exchange membrane toward metallic ions. Transference fluxes have been determined either as experimental values or calculated according to theoretical models. A good agreement between theoretical and experimental flows has been obtained principally in the case of CMV membrane which presents a lower thickness. It has been demonstrated that addition of thiourea causes an increase of separation properties of membrane. The separation is mainly due to the complex formation between Ag⁺ and Cu⁺ ions and thiourea. Monovalent copper ion is obtained after reduction of Cu²⁺ and oxidation of thiourea and formation of bisulfide of formamidine which constitute a barrier to monovalent complex transference.