Studies on pyrrolidinones. On the application of copper-catalyzed arylation of methyl pyroglutamate to obtain a new benzo[de]quinoline scaffold

Optimized conditions for copper-catalyzed N-arylation of methyl pyroglutamate are described. These studies permitted the synthesis of methyl N-naphthylpyroglutamate, which was then cyclized to a ketone. The known dehydration of amidoketones by PPA was extended to this new scaffold to lead to a novel condensed benzo[de]quinoline with potential antioxidative activity.     

Development and validation of a dried blood spot–HPLC assay for the determination of metronidazole in neonatal whole blood samples

A selective and sensitive high-performance liquid chromatography method with UV detection for the determination of metronidazole in dried blood spots (DBS) has been developed and validated. DBS samples [spiked or patient samples] were prepared by applying blood (30 µL) to Guthrie cards. Discs (6 mm diameter) were punched from the cards and extracted using water containing the internal standard, tinidazole. The extracted sample was chromatographed without further treatment using a reversed phase system involving a Symmetry® C18 (5 µm, 3.9?×?150 mm) preceded by a Symmetry® guard column of matching chemistry and a detection wavelength of 317 nm. The mobile phase comprised acetonitrile/0.01?M phosphate solution (KH₂PO₄), pH 4.7, 15:85, v/v, with a flow rate of 1 mL/min. The calibration was linear over the range 2.5–50 mg/mL. The limits of detection and quantification were 0.6 and 1.8 µg/mL, respectively. The method has been applied to the determination of 203 DBS samples from neonatal patients for a phamacokinetic/pharmacodynamic study.     

Adventitious formation of a new oxopentadienyl Mn(I) tricarbonyl complex: Structural study and bonding investigation of (η-CH2C(Fc)CHC(Fc)O)Mn(CO)3

A Mn(I) tricarbonyl complex of a 1,3-diferrocenyl-1-oxopentadienyl ligand was synthesised adventitiously by what seems to be an in-situ aldol-like condensation of two acetylferrocene units promoted by benzyl-Mn(CO)₅. X-ray structural analysis of this unexpected product confirms the η⁵ coordination of the 1,3-diferrocenyl-1-oxopentadienyl ligand to the Mn(CO)₃ moiety. The nature of the metal-ligand bonding relationship was studied by theoretical calculations; it outlines the charge unbalance (polarisation) at the oxopentadienyl moiety as well as the lack of ketone character of the latter Mn-bound ligand.     

Crystal structures of the novel hydrated borates Ba2B5O9(OH), Sr2B5O9(OH) and Li2Sr8B22O41(OH)2

Three novel hydrated borates Ba₂B₅O₉(OH) (1), Sr₂B₅O₉(OH) (2) and Li₂Sr₈B₂₂O₄₁(OH)₂ (3) have been synthesized hydrothermally and their structures determined. Compounds (1) and (2) are isostructural, crystallizing in space group P2₁/c and having lattice parameters of a=6.6330(13) Å, b=8.6250(17) Å, c=14.680(3) Å, β=93.46(3)° and a=6.4970(13) Å, b=8.4180(17) Å, c=14.177(3) Å, β=94.35(3)°, respectively. Compound (3) crystallizes in P-1 with lattice parameters of a=6.4684(13) Å, b=8.4513(17) Å, c=14.881(3) Å, α=101.21(3)°, β=93.96(3)°, γ=90.67(3)°. While similar in their axis lengths, (3) differs greatly in structure and formulation from (1) and (2). The structure of (1) and (2) is contrasted to that of the well-known mineral hilgardite (Ca₂B₅O₉Cl·H₂O).     

High speeds complementary integrated circuits fabricated with all‐printed polymeric semiconductors

Inkjet‐printed high speed polymeric complementary circuits are fabricated using an n‐type ([poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐dithiophene)} [P(NDI2OD‐T2), Polyera ActivInk N2200] and two p‐type polymers [poly(3‐hexylthiophene) (P3HT) and a dithiophene‐based polymer (Polyera ActivInk P2100)]. The top‐gate/bottom‐contact (TG/BC) organic field‐effect transistors (OFETs) exhibit well‐balanced and very‐high hole and electron mobilities (μ_FET) of 0.2–0.5 cm²/Vs, which were enabled by optimization of the inkjet‐printed active features, small contact resistance both of electron and hole injections, and effective control over gate dielectrics and its orthogonal solvent effect (selection of poly(methyl methacrylate) and 2‐ethoxyethanol). Our first demonstrated inkjet‐printed polymeric complementary devices have been integrated to high‐performance complementary inverters (gain >30) and ring oscillators (oscillation frequency ～50 kHz). We believe that the operating frequency of printable organic circuits can be further improved more than 10 MHz by fine‐tuning of the device architecture and optimization of the p‐ and n‐channel semiconductor processing. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Mereologies as the grammars of chemical discourses

Mereology is the logic of part—whole concepts as they are used in many different contexts. The old chemical metaphysics of atoms and molecules seems to fit classical mereology very well. However, when functional attributes are added to part specifications and quantum mechanical considerations are also added, the rules of classical mereology are breached in chemical discourses. A set theoretical alternative mereology is also found wanting. Molecular orbital theory requires a metaphysics of affordances that also stands outside classical mereology.     

Electrochemical genosensor based on three-dimensional DNA polymer brushes monolayers

A new approach to the three dimensional integration of short DNA strands at gold electrode surfaces via the in situ formation of DNA-acrylamide conjugates is presented. Surface initiated atom transfer radical polymerisation was employed to grow acrylamide brushes co-polymerised in the presence of acrylamide modified DNA probes. This strategy was demonstrated for the realisation of biofunctionalised thin polymer films capable of binding its complementary 105-base DNA amplicon. The synthesised brushes were characterised using atomic force microscopy, attenuated total reflectance spectroscopy and electrochemical impedance spectroscopy. Once characterised, the polymer brushes were applied to the quantitative detection of target DNA using an enzyme labelled reporter DNA probe in a sandwich-type format.     

A trading mechanism contingent on several indices

We introduce a trading mechanism where the execution of an order on a security can be made contingent on the relation between the clearing price of the security and the clearing price of one or several indices. A mechanism similar to ours, but limited to only one index, was implemented on the Tel Aviv Stock Exchange. We argue that it is in some cases crucial to make the execution of an order contingent on several indices. Our mechanism consists of a particular implementation of a double-sided multi-unit combinatorial auction with substitutes (or DMCS auction), which we introduced in an earlier article.