Straightforward Synthesis of (R,S)-β-Methyleneaspartic Acid, an Inhibitor of Glutamate-Aspartate Transaminase

Summary. A Baylis-Hillman adduct of methyl acrylate and ethyl glyoxalate was converted into the trichloroacetimidate that in the presence of DABCO rearranged to the corresponding trichloroacetamide. Eventually, hydrolysis under acidic conditions, led to the hydrochloride of racemic β-methyleneaspartic acid.     

Pyrrolic tripodal receptors for carbohydrates. Role of functional groups and binding geometry on carbohydrate recognition

The contribution from several H-bonding groups and the impact of geometric requirements on the binding ability of benzene-based tripodal receptors toward carbohydrates have been investigated by measuring the affinity of a set of structures toward octyl β-D-glucopyranoside, selected as a representative monosaccharide. The results reported in the present study demonstrate that a judicious choice of correct geometry and appropriate functional groups is critical to achieve the complementary hydrogen bonding interactions required for an effective carbohydrate recognition.     

On examples in mathematical thinking and learning

The importance of examples and exemplification in mathematical thinking, learning and teaching, is well recognized by mathematicians, epistemologists and mathematics educators. In the collection of papers on these topics presented in this issue, we aim to contribute to the debate on this theme, proposing original studies carried out from different approaches and perspectives, and linked to other relevant topics within mathematics education.     

To exist or not to exist: example generation in Real Analysis

This article deals with the activity of example generation as a special case of problem solving. We asked university students in the scientific-technological area to produce examples (which may exist or not) of mathematical objects fulfilling given requirements. For the analysis of students’ performances, we have developed a model that attempts to grasp the nature of the different stages in the solving process. The discussion of the findings allows us to outline specificities and educational potentialities of example generation activities.     

A novel base-mediated intramolecular hydroamination to build fused heteroaryl pyrazinones

Functionalized fused heteroaryl pyrazinones were built up through a novel DBU-catalyzed intramolecular hydroamination reaction of aryl(prop-2-yn-1-yl)-1H-heteroaryl-2-carboxamides. The nucleophilic addition afforded three isomers; two with an exo-cyclic double bond [cis (Z), trans (E)], and a third one with an endo-cyclic double bond. After the carboxamide deprotection, isomerization of the mixture under acidic conditions resulted in a unique isomer.     

Zinc Oxide Thin Films for Memristive Devices: A Review

Zinc Oxide (ZnO) thin films have been addressed as promising candidates for the fabrication of Resistive Random Access Memory devices, which are alternative to conventional charge-based flash memories. According to the filamentary conducting model and charge trapping/detrapping theory developed in the last decade, the memristive behavior of ZnO thin films is explained in terms of conducting filaments formed by metallic ions and/or oxygen vacancies, and their breaking through electrochemical redox reactions and/or recombination of oxygen vacancies/ions. A comparative review of the memristive properties of ZnO thin films grown by sputtering, atomic layer deposition (ALD), pulsed laser deposition (PLD), and sol-gel methods is here proposed. Sputtered ZnO thin films show promising resistive switching behaviors, showing high on/off ratios (10–10⁴), good endurance, and low operating voltages. ALD is also indicated to be useful for growing conformal ZnO layers with atomic thickness control, resulting in important resistive switching characteristics, such as relatively high on/off ratios and low operating voltages. High insulating epitaxial ZnO thin films can be obtained by PLD, showing reliable switching properties at low voltages and with good retention. On the contrary, the sol-gel approach generally results in ZnO thin films with poor resistive switching behaviors. Nevertheless, thin films derived from ZnO NPs show improved switching performances, with higher on/off ratios and lower operating voltages. Independently of the synthetic approach, doped ZnO thin films exhibit better resistive switching behaviors than pristine ones, coupling a strong increase of the on/off ratio with a more stable switching response.     

Phantom validation and in vivo application of an inversion procedure for retrieving the optical properties of diffusive layered media from time-resolved reflectance measurements

An experimental validation of an inversion procedure for retrieving the optical properties of layered media from multidistance time-resolved reflectance measurements is presented. The results cover a wide range of optical properties, showing excellent effectiveness and reliability of the procedure in reconstructing the optical properties of a two-layered medium. The optical properties of the first layer and the absorption of the second layer could be retrieved with excellent precision, whereas the reduced scattering coefficient of the second layer was reconstructed with a large error. The first layer thickness could be retrieved with an error less than 50%. An example of retrieval of the optical properties of muscle from in vivo measurements during an arterial occlusion is shown.     

Imparting Nonfouling Properties to Chemically Distinct Surfaces with a Single Adsorbing Polymer: A Multimodal Binding Approach

Surface‐active polymers that display nonfouling properties and carry binding groups that can adsorb onto different substrates are highly desirable. We present a postmodification protocol of an active‐ester‐containing polymer that allows the creation of such a versatile platform. Poly(pentafluorophenyl acrylate) has been postmodified with a fixed grafting ratio of a nonfouling function (mPEG) and various combinations of functional groups, such as amine, silane and catechol, which can provide strong affinity to two model substrates: SiO₂ and TiO₂. Adsorption, stability and resistance to nonspecific protein adsorption of the polymer films were studied. A polymer was obtained that maintained its surface functionality under a variety of harsh conditions. EG surface‐density calculations show that this strategy generates a denser packing when both negatively and positively charged groups are present within the backbone, and readily allows the fabrication of a broad combinatorial matrix.

     

An Outline of the Latest Crystallographic Studies on Inhibitor-Enzyme Complexes for the Design and Development of New Therapeutics against Tuberculosis

The elucidation of the structure of enzymes and their complexes with ligands continues to provide invaluable insights for the development of drugs against many diseases, including bacterial infections. After nearly three decades since the World Health Organization’s (WHO) declaration of tuberculosis (TB) as a global health emergency, Mycobacterium tuberculosis (Mtb) continues to claim millions of lives, remaining among the leading causes of death worldwide. In the last years, several efforts have been devoted to shortening and improving treatment outcomes, and to overcoming the increasing resistance phenomenon. The structural elucidation of enzyme-ligand complexes is fundamental to identify hot-spots, define possible interaction sites, and elaborate strategies to develop optimized molecules with high affinity. This review offers a critical and comprehensive overview of the most recent structural information on traditional and emerging mycobacterial enzymatic targets. A selection of more than twenty enzymes is here discussed, with a special emphasis on the analysis of their binding sites, the definition of the structure–activity relationships (SARs) of their inhibitors, and the study of their main intermolecular interactions. This work corroborates the potential of structural studies, substantiating their relevance in future anti-mycobacterial drug discovery and development efforts.     

The role of alkane dithiols in controlling polymer crystallization in small band gap polymer:Fullerene solar cells

The effect of the addition of 1,8‐octanedithiol (ODT) during processing on the microstructure of blend films of poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7(2,1,3‐benzothiadiazole)] (PCPDTBT) and [6,6]‐phenyl‐C₇₁ butyric acid methyl ester ([70]PCBM) is studied. Grazing incidence X‐ray diffraction and absorption spectroscopy show that the crystalline order of PCPDTBT increases when ODT is introduced in the solution phase either to neat polymer systems or to blends with [70]PCBM. The increased crystalline order is accompanied by less dispersive hole transport in the polymer, and leads to a more efficient formation of a percolating fullerene network within the blend. This contributes to an increase in photocurrent generation. However, the bimolecular recombination rate as determined from photovoltage transients increases upon addition of ODT, limiting the power conversion efficiency to values well below those expected from the energy levels of PCPDTBT. We propose some explanations for this increase in bimolecular recombination, based also on variable angle spectroscopic ellipsometry measurements. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011