(E)-1-alkyl-4-

(E)-1-Alkyl-4-[2-(alkylsulfonyl)-1-ethenyl]pyridinium salts were synthesized in two steps. These sulfones were stable at pH 7.3 and underwent a nucleophilic vinylic substitution (S(N)V) with mercaptans, including thiouracile, to give the corresponding 4-(thiovinyl)-pyridinium salts. The X-ray diffraction structure of (E)-1-methyl-4-[2-(ethylsulfanyl)-1-ethenyl]pyridinium iodide indicated conjugation of the sulfur with the pyridinium ring. (Z)-1-Methyl-4-[2-(methylsulfanyl)-1-ethenyl]pyridinium iodide, prepared from the corresponding thioether by reaction with methyl iodide in diethyl ether, underwent isomerization to the E isomer in a first-order reaction in deuterated [D6]DMSO with an activation energy of 14 kcalmol(-1). At pH 7, the (E)-1-methyl-4-[2-(methylsulfonyl)-1-ethenyl]pyridinium iodide (19) reacted specifically with thiols. The reaction of this sulfone with glutathione in a TES buffer at pH 7 was a second-order reaction (k = 4,100 M(-1)s(-1) at 30 degrees C) and gave the corresponding substitution product with an intense long wavelength absorption band (lambdamax=360 nm, epsilon = 27,500 M(-1)cm(-1)). The modification of different enzymes of known structure with 19 showed the high selectivity of this reagent towards thiol groups and its usefulness in the quantitative determination of free thiol groups in proteins.     

Exosome-Coated Zeolitic Imidazolate Framework Nanoparticles for Intracellular Detection of ATP

The intracellular delivery of metal-organic frameworks(MOFs)encapsulated with functional biomolecules represents a promising av-enue in the field of biomedicine...     

Switchable Q-switched and laser operating mode-locked erbium-doped fiber in the L-band region

We demonstrate a switchable Q-switched and mode-locked erbium-doped fiber laser （EDFL） operating in the L-band region using the nonlinear polarization rotation effect. The switching operation is achieved by controlling intensity-dependent loss using a polarization controller. In Q-switching mode, the EDFL produces a pulse train with a repetition rate of 21.1 kHz, pulse width of 7.7 #s, and pulse energy of 13.6 nJ. The EDFL also generates a multi-wavelength comb with a very narrow and constant wavelength spacing of 0.045 nm and optical signal-to-noise ratio of at least l0 dB. During mode locking, the EDFL produces stretched pulses with 3-dB bandwidth of 26.2 nm, pulse width of 350 fs, repetition rate of 2.38 MHz, and pulse energy of 48.56 pJ.     

Performance evaluation of polycyclic aromatic hydrocarbons analysis in sediment from proficiency testing with metrological reference values

This paper describes a metrological approach to evaluate the measurement capability of laboratories participating in two proficiency testing (PT) programmes involving the analysis of five polycyclic aromatic hydrocarbons (PAHs) in sediment samples. Reference values of PAHs in the programmes for performance assessment were obtained from an accurate isotope dilution gas chromatography mass spectrometry (ID-GCMS) method which was thoroughly validated and verified. Isotope dilution mass spectrometry (IDMS) technique usually has a well-defined measurement uncertainty budget and a traceability link to an International System of Units. Provision of the metrological reference values in PT enables the establishment of a technical platform to assess the actual competence of the participating laboratories in sediment PAHs analysis. Results of the PT programmes showed that about 80 % of the laboratories employed gas chromatography in their analyses and the remaining used liquid chromatography. Irrespective of the techniques being used, however, the majority of the participating laboratories were observed to underestimate values in which the mean values of the five reported PAHs were less than those of the ID-GCMS-derived reference values by 13–20 %. Only 41–44 % of the participating laboratories were able to achieve satisfactory z-scores. The present study revealed that the reinforcement of the capability for accurate measurement of PAHs in sediment samples in laboratories worldwide should be addressed.     

Effect of synthesis conditions on the mechanism of reversible inhibition in the TEMPO-mediated polymerization of 4-vinylpyridine

The effects of polymerization conditions (the types and concentrations of initiator and solvent, the TEMPO-to-initiator molar ratio, and temperature) on the kinetics and mechanism of pseudoliving radical polymerization of 4-vinylpyridine mediated by the nitroxide TEMPO are studied. The key quantitative parameters of the process are calculated: namely, the rate constant of reinitiation, the rate constant of inhibition, and the product of the propagation-rate constant and the pseudoliving equilibrium constant. The optimum conditions for the controlled synthesis of poly(4-vinylpyridine) mediated by TEMPO are ascertained.     

Inclusion of thymol into cucurbiturils: density functional theory approach with dispersion correction and natural bond orbital analysis

Journal of Inclusion Phenomena and Macrocyclic Chemistry - Stability of inclusion complexes of thymol (a natural flavour) with cucurbit[n]urils was interpreted by using density functional theory...