Efficient microwave combinatorial parallel and nonparallel synthesis of N-alkylated glycine methyl esters as peptide building blocks

An easy and convenient microwave-assisted synthesis of N-alkylated glycine methyl esters is described. Parallel and nonparallel combinatorial methods are described and compared. The described reactions are reductive alkylations of several aldehydes and glycine methyl ester in the presence of NaBH3CN. Good yields and short reaction times are the main aspects of these procedures.     

Microwave-assisted synthesis of 1,3-dihydro-[1,2,5]thiadiazolo[3,4-b]pyrazine-2,2-dioxides

1,3-Dihydro[1,2,5]thiadiazolo[3,4-b]pyrazine-2,2-dioxides are obtained in a good yield from the reaction of 2,3-diamino pyrazines with sulfamide under microwave conditions.     

Structural and spectroscopic studies of nickel(II) complexes with a library of Bis(oxime)amine-containing ligands

A library of tripodal amine ligands with two oxime donor arms and a variable coordinating or noncoordinating third arm has been synthesized, including two chiral ligands based on l-phenylalanine. Their Ni(II) complexes have been synthesized and characterized by X-ray crystallography, UV-vis absorption, circular dichroism, and FTIR spectroscopy, mass spectrometry, and room-temperature magnetic susceptibility. At least one crystal structure is reported for all but one Ni/ligand combination. All show a six-coordinate pseudo-octahedral coordination geometry around the nickel center, with the bis(oxime)amine unit coordinating in a facial mode. Three distinct structure types are observed: (1) for tetradentate ligands, six-coordinate monomers are formed, with anions and/or solvent filling out the coordination sphere; (2) for tridentate ligands, six-coordinate monomers are formed with Ni(II)(NO(3))(2), with one monodentate and one bidentate nitrate filling the remaining coordination positions; (3) for tridentate ligands, six-coordinate, bis(mu-Cl) dimers are formed with Ni(II)Cl(2), with one terminal and two bridging chlorides filling the coordination sphere. The UV-vis absorption spectra of the complexes show that the value of 10 Dq varies according to the nature of the third arm of the ligand. The trend based on the third arm follows the order alkyl/aryl < amide < carboxylate < alcohol < pyridyl < oxime.     

Synthesis of unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes via alkylidene carbenoid rearrangements

Unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes are synthesized in four steps from commercially available aldehydes or carboxylic acids. The key step in this process involves a Fritsch-Buttenberg-Wiechell rearrangement, in which an alkylidene carbenoid intermediate subsequently rearranges to the desired polyyne. This rearrangement proceeds under mild conditions, and it is tolerant of a range of functionalities. In general, the procedurally facile formation of the dibromoolefinic precursors, in combination with the effectiveness of the rearrangement step, makes this procedure an attractive alternative to traditional methods for di- and triyne synthesis that utilize palladium or copper catalysis.     

A highly selective route to beta-C-glycosides via nonselective samarium iodide induced coupling reactions

Stereoselective preparation of beta-C-glycosides has been developed from acetylated glycopyranosyl 2-pyridyl sulfones, involving a samarium-Barbier coupling procedureoxidation-isomerization sequence.     

Studies of polyester fiber as carrier for microbes in a quantitative test method for disinfectants

Tests were conducted by a Task Force on Disinfectant Test Methods that was appointed to investigate controversies regarding the accuracy of AOAC test methods for disinfectants as presented in AOAC's Official Methods of Analysis, Chapter 6. The general principles for new and improved AOAC tests are discussed, and a disinfectant test using microbes labeled onto a polyester fiber surface is described. The quantitative test measures the survival of test microbes as a function of exposure time as well as the exposure conditions required to kill 6 log10 of the test microbes. The time required was similar to that for the kinetics of the kill of Bacillus subtilis-labeled cylinders as tested by methods of the AOAC Sporicidal Test 966.04.     

Synthesis and conformational analysis of a ribo-type cyclohexenyl nucleoside

A straightforward approach to a novel class of ribo-type cyclohexenyl nucleosides is described. An electron-demand Diels-Alder reaction forms the key-step of the chosen synthetic pathway. Although the difference is small, conformational analysis using NMR shows that this nucleoside analogue adopts preferentially an 2H3 conformation (S-type), while the "deoxy" cyclohexenyl analogue has a preference for a C3' endo conformation (N-type). Analyses of the conformational equilibrium reveal that, in the given experimental conditions, the difference between adenosine and its cyclohexenyl congener resides in their different DeltaG values; furthermore, in adenosine, the conformational preference is of enthalpic origin, whereas in the cyclohexenyl congener, the conformational preference is of entropic origin.     

Advanced chiral molecular media for enantioselective electrochemistry and electroanalysis

An increasing number of strategies and tools have been proposed to endow the electrochemical interphase with chirality, to achieve enantiodiscrimination in analytical and/or preparative applications. So far, chirality has mostly been implemented not only at the electrode surface side but also on the medium one. Recently, the attractiveness of the latter approach has remarkably increased on account of the increasing availability of advanced chiral molecular media with intrinsic attractive features for electrochemistry applications, such as chiral ionic liquids, chiral ionic liquid crystals, and chiral deep eutectic solvents. With respect to solid layer/fixed chiral networks, advanced chiral media can still offer a reasonably high degree of local structuring, while being less demanding concerning preparation and management protocols, as well as less sensitive to fouling/regeneration issues. Different ways to implement chirality in advanced molecular media, including cases of powerful ‘inherent chirality,’ will be presented and discussed, particularly focusing on recent applications in the electrochemical field.     

Middleman covert channel establishment based on MORE routing protocol using network coding in ad hoc networks

Covert channels have been recently the subject of the study in both creation and countermeasure aspects. There are many different ways to embed the covert data in network standards and protocols, especially in wireless networks. MORE (MAC‐independent opportunistic routing) is an opportunistic routing protocol which uses networks coding to enhance routing performance by reducing the repetitions. This protocol can be a suitable medium for covert channel establishment. A middleman covert channel establishment method is proposed in this paper over MORE routing protocol and with the use of network coding. Hidden data are transferred through packet's payload bytes. Covert sender manipulates coding mechanism by calculating packets' coefficients instead of random selection. The proposed covert channel provides the average throughput of 218 and 231 bps, using two different data length approaches which is relatively a good comparing to the previous network layer covert channels. The proposed covert channel is also a covert storage channel and cannot be removed or restricted. Effect of different network characteristics on the proposed method's capacity and security is investigated by a simulation study, and the results are discussed.     

Size-based separations of proteins by capillary electrophoresis using linear polyacrylamide as a sieving medium: model studies and analysis of cider proteins

Electrophoretic conditions to separate sodium dodecyl sulfate (SDS)-protein complexes according to their relative molecular mass by capillary electrophoresis (CE) using linear polyacrylamide as a sieving matrix were examined. Five purified proteins with relative molecular masses between 14 400 and 66 200 Da were separated on a coated fused-silica capillary with an internal diameter of 100 microm and an effective length of 24 cm (total length, 32.5 cm). Benzoic acid was added to the solution of purified proteins as internal standard; beta-mercaptoethanol was also added as reducing agent. The running buffer composition was 0.05 M tris(hydroxymethyl)aminomethane (Tris), 0.035 M aspartic acid, 0.1% m/v SDS, 4% m/v acrylamide, the resulting pH being 8.0. The applied voltage was 7 kV (reversed voltage polarity) in order to avoid high current intensities. Under optimized conditions, the five proteins were separated in less than 15 min, with a % relative standard deviation (RSD) between 0.2 and 0.4 for migration times in the same day. Good efficiency (values between 150 000 and 40 000 N/m) and resolution (values between 2 and 2.8) were obtained. The inverse of relative migration times was found to correlate with the logarithm of their relative molecular mass. Finally, cider proteins were analyzed and their relative molecular masses were determined. These results were compared with those obtained by SDS-polyacrylamide gel electrophoresis (SDS-PAGE).