Synthesis and antimicrobial activity of substituted [(pyrazol‐4‐yl)methylene]hydrazono‐2,3‐dihydrothiazoles and their sugar derivatives

A number of new [(pyrazol‐4‐yl)methylene]hydrazono‐2,3‐dihydrothiazole derivatives, their sugar hydrazones and N‐glycosides were synthesized. Furthermore, N‐substituted oxygenated alkyl and hydroxyl derivatives and 1,3,4,‐oxadiazoline acyclic nucleoside analogs were prepared. The newly synthesized compounds were tested for their antimicrobial activities and showed moderate to high inhibition activities. J. Heterocyclic Chem., (2012).     

Synthesis and Antimicrobial Activity of New 1,2,3‐Triazolopyrimidine Derivatives and Their Glycoside and Acyclic Nucleoside Analogs

New [1,2,4‐oxadiazolyl]methyl‐3H‐[1,2,3]triazolo[4,5‐d]pyrimidin derivatives were synthesized starting from N′‐Hydroxy‐1‐naphthimidamide. The N‐substituted acyclic nucleoside analogs as well as the substituted glycosides were also prepared by reaction with the corresponding reagents. The antimicrobial results indicated that most of the tested compounds exhibited moderate to high antimicrobial activity whereas few compounds were found to exhibit little or no activity against the tested microorganisms.     

Chlorobiphenyls in sewage sludge; comparison of extraction methods

Six extraction methods for the analysis of PCBs (CB-28, CB-52, CB-101, CB-118, CB-138, CB-153 and CB-180) in sewage sludge were tested. A certified reference material (CRM 392) was used for the evaluation of the performance of the methods. Soxhlet-Dean-Starch with toluene as solvent, Soxhlet with hexane:acetone (2:3), cold digestion/saponification with 2 mol/L KOH in methanol followed by partition with hexane, and sonicated liquid-solid extraction with hexane:acetone (1:1) produced accurate results (97%, 93%, 104%, and 88%, respectively) with acceptable precisions (6.2%, 6.8%, 15% and 12%, respectively). Results in close agreement with the certified value for all congeners were obtained by treatment with BF₃-methanol prior to partition with dichloromethane. However, this is a tedious procedure and involves the use of hazardous compounds. Cyclic steam distillation produced results with an accuracy of around 80% and a good precision (5.2%). The very low consumption of solvents and other expensive chemicals by this technique and the possibility of analyzing the extract directly without clean-up make it an interesting alternative to the more sophisticated methods. Column elution with dichloromethane was found to be less efficient (61%), but it is a rapid, direct method with a low consumption of solvents and it may therefore serve as screening method. Received: 29 April 1997 / Revised: 30 July 1997 / Accepted: 6 August 1997     

Halogen-substituted thiophenol molecules on Cu(111)

Para-halosubstituted thiophenols (X-TPs, where X is Br, Cl, or F) form ordered islands and monolayers on Cu(111) at temperatures as low as 81 K. At incomplete coverages, all X-TPs adsorb with the dehydrogenated thiol group attached to the substrate and the substituted ring inclined toward the surface, as verified experimentally and theoretically. The structure of ordered islands has a pronounced dependence on the nature of the halogen substituent: while unsubstituted TP and pentafluoro-TP molecules do not self-assemble into extended ordered patterns at 81 K, X-TP molecules form a range of different structures which depend both on the size and electronegativity of the substituent, as well as on the coverage.     

An efficient and mild protocol for the synthesis of unsymmetrical ureas in the absence of catalyst and additives

<正>A new practical method for the synthesis of unsymmetrical ureas was achieved by reaction of phenylurea with primary and secondary amines under neutral and mild condition in very good yields.The reaction took place in refluxing dioxane and does not require any catalyst or additives.     

Characterization and de novo sequencing of snow crab tropomyosin enzymatic peptides by both electrospary ionization and matrix‐assisted laser desorption ionization QqToF tandem mass spectrometry

The protein tropomyosin (TM) is a known major allergen present in shellfish causing frequent food allergies. TM is also an occupational allergen generated in the working environment of snow crab (Chionoecetes opilio) processing plants. The TM protein was purified from both claw and leg meats of snow crab and analyzed by electrospray ionization and matrix‐assisted laser desorption/ionization (MALDI) using hybrid quadruple time‐of‐flight tandem mass spectrometry (QqToF‐MS). The native polypeptide molecular weight of TM was determined to be 32 733 Da. The protein was further characterized using the ‘bottom‐up’ MS approach. A peptide mass fingerprinting was obtained by two different enzymatic digestions and de novo sequencing of the most abundant peptides performed. Any post‐translational modifications were identified by searching their calculated and predicted molecular weights in precursor ion spectra. The immunological reactivity of snow crab extract was evaluated using specific antibodies and allergenic reactivity assessed with serum of allergic patients. Subsequently, a signature peptide for TM was identified and evaluated in terms of identity and homology using the basic local alignment search tool (BLAST). The identification of a signature peptide for the allergen TM using MALDI‐QqToF‐MS will be critical for the sensitive and specific quantification of this highly allergenic protein in the work place. Copyright © 2010 John Wiley & Sons, Ltd.     

Highly sensitive and selective amperometric sensors for nanomolar detection of iodate and periodate based on glassy carbon electrode modified with iridium oxide nanoparticles

Iridium oxide nanoparticles are grown on a glassy carbon electrode by electrodepositing method. The electrochemical behavior and electrocatalytic activity of modified electrode towards reduction of iodate and periodate are studied. The reductions of both ions occur at the unusual positive peak potential of 0.7 V vs. reference electrode. The modified electrode is employed successfully for iodate and periodates detection using cyclic voltammetry, hydrodynamic amperometry and flow injection analysis (FIA). In the performed experiments, flow injection amperometric determination of iodate and periodate yielded calibration curves with the following characteristics: linear dynamic range up to 100 and 80 μM, sensitivity of 140.9 and 150.6 nA μM⁻¹ and detection limits of 5 and 36 nM, respectively. The repeatability of the modified electrode for 21 injections of 1.5 μM of iodate solution is 1.5%. The interference effects of NO₂⁻, NO₃⁻, ClO₃⁻, BrO₃⁻, ClO₄⁻, SO₄²⁻, Cu²⁺, Zn²⁺, Mn²⁺, Mg²⁺, Cd²⁺, Ca²⁺, Na⁺, K⁺, NH₄⁺ and K⁺, CH₃COO⁻ and glucose were negligible at the concentration ratio of more than 1000. The obtained attractive analytical performance together with high selectivity and simplicity of the proposed method provide an effective and e novel modified electrode to develop an iodate and periodate sensor. Sensitivity, selectivity, the liner concentration range and the detection limit of the developed sensor are all much better than all known similar sensors in the literature for iodate and periodate determination.     

Extraction of biogenic amines using sorbent materials containing immobilized crown ethers

Three sorbent materials (A18C6-MS, DA18C6-MS and AB18C6-MS) based on the crown ether ligands, 1-aza-18-crown-6, 1,4,10,13-tetraoxa-7,16-diazacyclo octadecane and 4′-aminobenzo-18-crown-6, respectively, were prepared by the chemical immobilization of the ligand onto mesoporous silica support. The sorbents were characterized by FT-IR, scanning electron microscopy-energy dispersive X-ray microanalysis, elemental analysis and nitrogen adsorption-desorption test. The applicability of the sorbents for the extraction of biogenic amines by the batch sorption method was extensively studied and evaluated as a function of pH, biogenic amines concentration, contact time and reusability. Under the optimized conditions, all the sorbents exhibited highest selectivity toward spermidine (SPD) compared to other biogenic amines (tryptamine, putrescine, histamine and tyramine). Among the sorbents, AB18C6-MS offer the highest capacity and best selectivity towards SPD in the presence of other biogenic amines. The AB18C6-MS sorbent can be repeatedly used three times as there was no significant degradation in the extraction of the biogenic amines (%E > 85). The optimized procedure was successfully applied for the separation of SPD in food samples prior to the reversed-phase high performance liquid chromatography separation.     

Cyclization vs. Elimination Reactions of 5‐Aryl‐5‐hydroxy 1,3‐Diones: One‐Pot Synthesis of 2‐Aryl‐2,3‐dihydro‐4H‐pyran‐4‐ones

2‐Aryl‐2,3‐dihydro‐4H‐pyran‐4‐ones were prepared in one step by cyclocondensation of 1,3‐diketone dianions with aldehydes. The use of HCl (10%) for the aqueous workup proved to be very important to avoid elimination reactions of the 5‐aryl‐5‐hydroxy 1,3‐diones formed as intermediates. The TiCl₄‐mediated cyclization of a 2‐aryl‐2,3‐dihydro‐4H‐pyran‐4‐one with 1,3‐silyloxybuta‐1,3‐diene resulted in cleavage of the pyranone moiety and formation of a highly functionalized benzene derivative.     

Molecular characterization of <Emphasis Type="Italic">tlyA</Emphasis> gene product,Rv1694 of <Emphasis Type="Italic">Mycobacterium tuberculosis</Emphasis>: A non-conventional hemolysin and a ribosomal RNA methyl transferase

Background  

Mycobacterium tuberculosis is a virulent bacillus causing tuberculosis, a disease responsible for million deaths each year worldwide. In order to understand its mechanism of pathogenesis in humans and to help control tuberculosis, functions of numerous Mycobacterium tuberculosis genes are being characterized. In this study we report the dual functionality of tlyA gene product of Mycobacterium tuberculosis annotated as Rv1694, a 268 amino acid long basic protein.