Suppression of Anderson localization in disordered metamaterials

We study wave propagation in mixed, 1D disordered stacks of alternating right- and left-handed layers and reveal that the introduction of metamaterials substantially suppresses Anderson localization. At long wavelengths, the localization length in mixed stacks is orders of magnitude larger than for normal structures, proportional to the sixth power of the wavelength, in contrast to the usual quadratic wavelength dependence of normal systems. Suppression of localization is also exemplified in long-wavelength resonances which largely disappear when left-handed materials are introduced.     

Terahertz emission from collapsing field domains during switching of a gallium arsenide bipolar transistor

Broadband pulsed THz emission with peak power in the sub-mW range has been observed experimentally during avalanche switching in a gallium arsenide bipolar junction transistor at room temperature, while significantly higher total generated power is predicted in simulations. The emission is attributed to very fast oscillations in the conductivity current across the switching channels, which appear as a result of temporal evolution of the field domains generated in highly dense electron-hole plasma. This plasma is formed in turn by powerful impact ionization in multiple field domains of ultrahigh amplitude.     

The mechanochemical Friedel-Crafts polymerization as a solvent-free cross-linking approach toward microporous polymers

Herein we report the mechanochemical Friedel-Crafts alkylation of 1,3,5-triphenylbenzene (TPB) with two organochloride cross-linking agents, dichloromethane (DCM) and chloroform (CHCl₃), respectively. During a thorough milling parameter evaluation, the DCM-linked polymers were found to be flexible and extremely sensitive toward parameter changes, which even enables the synthesis of a polymer with a SSA_BET of 1670 m²/g, on par with the solution-based reference. Contrary, CHCl₃-linked polymers are exhibiting a rigid structure, with a high porosity that is widely unaffected by parameter changes. As a result, a polymer with a SSA_BET of 1280 m²/g could be generated in as little as 30 minutes, outperforming the reported literature analogue in terms of synthesis time and SSA_BET. To underline the environmental benefits of our fast and solvent-free synthesis approach, the green metrics are discussed, revealing an enhancement of the mass intensity, mass productivity and the E-factor, as well as of synthesis time and the work-up in comparison to the classical synthesis. Therefore, the mechanochemical polymerization is presented as a versatile tool, enabling the generation of highly porous polymers within short reaction times, with a minimal use of chlorinated cross-linker and with the possibility of a post polymerization modification.     

Electrochemical Synthesis of gem-Difluoro- and γ-Fluoro-Allyl Boronates and Silanes

The electrochemical synthesis of fluorinated allyl silanes and boronates was disclosed. The addition of electrogenerated boryl or silyl radicals onto many α-trifluoromethyl or α-difluoromethylstyrenes in an undivided cell allowed the formation of a large panel of synthetically useful gem-difluoro and γ-fluoroallyl boronates and silanes (64 examples, from 31 % to 95 % yield). In addition, a scale up of the reactions under continuous flow was showcased using an electrochemical reactor with promising volumetric productivity (688 g.L⁻¹.h⁻¹ and 496 g.L⁻¹.h⁻¹). Moreover, the synthetic utility of these building blocks was highlighted through versatile transformations. Finally, plausible reaction mechanisms were suggested to explain the formation of the products.     

Control of the morphology and particle size of boehmite nanoparticles synthesized under hydrothermal conditions

The spontaneous nucleation under hydrothermal conditions often leads to aggregation of crystallizing particles, which is an undesired phenomenon when the goal is the preparation of nanocrystals with narrow particle size distribution. The present paper reports on the synthesis of boehmite nanocrystals under hydrothermal conditions. An aqueous aluminum chloride salt solution was first prepared, and the pH was increased to 11 using a 5 M sodium hydroxide solution. The hydrothermal treatment was performed at 160 degrees C for different periods of time. The system yielded relatively small (15-40 nm) boehmite crystallites aggregated into larger (160 nm) particles. To avoid the aggregation, a biocompatible polymer, sodium polyacrylate (NaPa) 2100, was employed as a size-/morphology-controlling agent. Thus, stable colloidal suspensions of rounded boehmite nanoparticles having a size between 15 and 40 nm were obtained at 160 degrees C for 24 h. Further, the effect of synthesis time on the morphological features of boehmite synthesized in such a NaPa-containing system was investigated. The increase of the synthesis time from 24 to 168 h resulted in the formation of very long boehmite fibers (1000-2000 nm) with an average diameter of about 10 nm. The boehmite samples were characterized by XRD, DLS, TEM, IR, N2 adsorption, and zeta potential measurements. The colloidal stability of the obtained suspension was also studied.     

cis-decalins from quinic acid: toward a synthesis of branimycin

[reaction: see text] Starting from (-)-quinic acid an efficient synthesis of highly functionalized cis-alpha,beta-unsaturated ketone 3, an advanced precursor of branimycin, has been accomplished via two key step reactions: a ring closing metathesis reaction to prepare the cis-decalin system, and a highly stereoselective epoxidation reaction.     

Combinatorial synthesis and characterization of new asymmetric porphyrins as potential photosensitizers in photodynamic therapy

Porphyrins play a major role as active photosensitizers in noninvasive optical photodynamic therapy (PDT). In a modular approach, this paper presents a short review of the recent developments of porphyrin structures and materials with improved photosensitizing properties and then presents the synthesis and characterization of a series of new second generation asymmetrical meso-tetraphenylporphyrins varied by substituent in the meta positions of the phenyl rings with either -OH or -OCH3 groups, whereas in the para positions only with -OCH3 groups. The new series of differentially functionalized porphyrins were obtained by a combinatorial multicomponent synthesis (Adler-Longo method) by simultaneously using two different aldehydes: 3,4-dimethoxybenzaldehyde and 3-hydroxybenzaldehyde. The porphyrins were isolated, purified and characterized by HPLC, TLC, UV-vis, fluorescence, MS, 1H-NMR, and 13C-NMR analysis, accompanied by DEPT 135 experiments. Because of the fact that the medium in cancerous tissues is often more acidic than in normal tissues, the capacity of these porphyrins to exist simultaneously in aggregated and protonated forms was also investigated, in tetrahydrofuran (THF) and acid THF-water systems, underlying the changes in the photophysical behaviour. The relative fluorescence quantum yields (Phif) were calculated in comparison with meso-tetraphenylporphyrin (TPP), and the values between 0.14-0.26 were found to be promising for further trials. The series of asymmetrically substituted tetraphenylporphyrins, as the new class of supramolecular materials, are suitable for further functionalization in order to improve their photophysical properties, and they could represent interesting potential PDT photosensitizers.     

Frequency doubling of CO2 laser radiation at 10.6 microm in the highly nonlinear chalcopyrite LiGaTe2

Type-I phase matching for second-harmonic generation at 10.6 microm in LiGaTe(2) is demonstrated by using a tunable single-frequency continuous-wave CO(2) laser, and the nonlinear coefficient of LiGaTe(2) is determined from comparison with AgGaSe(2). The effective nonlinearity of LiGaTe(2) for this process amounts to 34.5 pm/V.     

Antimicrobial and antileishmanial xanthones from the stem bark of <Emphasis Type="Italic">Allanblackia gabonensis</Emphasis>

The phytochemical study of the stem bark of Allanblackia gabonensis has resulted in the isolation and characterization of one new xanthone derivative, named allanxanthone D, together with ten known compounds, including six xanthone derivatives, allanxanthone A, 1,5-dihydroxyxanthone, 1,7-dihydroxyxanthone and 1,3,6,7-tetrahydroxy-2-(3-methylbut-2-enyl)xanthone, forbexanthone, 6-deoxyisojacareubin, one polyisoprenylated benzophenone, guttiferone F, one flavanol, epicathechin, two phytosterols, β-sitosterol, and campesterol. The structures of these compounds were established on the basis of one- and two-dimensional NMR homo- and heteronuclear evidence. These compounds were evaluated for their activity against Leishmania amazonensis in vitro and antimicrobial activities against a range of Gram-negative and Gram-positive bacteria. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 471–475, September-October, 2008.     

A route toward the generation of thermally stable Au cluster anions supported on the MgO surface

On the basis of experimental evidence and DFT calculations, we propose a simple yet viable way to stabilize and chemically activate gold nanoclusters on MgO. First the MgO surface is functionalized by creation of trapped electrons, (H (+))(e (-)) centers (exposure to atomic H or to H 2 under UV light, deposition of low amounts of alkali metals on partially hydroxylated surfaces, etc.); the second step consists in the self-aggregation of gold clusters deposited from the gas phase. The calculations show that the (H (+))(e (-)) centers act both as nucleation and activation sites. The process can lead to thermally stable gold cluster anions whose catalytic activity is enhanced by the presence of an excess electron.