Flexibility and swing effect on the adsorption of energy-related gases on ZIF-8: combined experimental and simulation study

ZIF-8, a prototypical zeolitic porous coordination polymer, prepared via the self-assembly of tetrahedral atoms (e.g. Zn and Co) and organic imidazolate linkers, presents large cavities which are interconnected by narrow windows that allow, in principle, molecular sieving. However, ZIF-8 shows flexibility due to the swing of the imidazolate linkers, which results in the adsorption of molecules which are too large to fit through the narrow window. In this work, we assess the impact of this flexibility, previously only observed for nitrogen, and the level of agreement between the experimental and simulated isotherms of different energy-related gases on ZIF-8 (CO(2), CH(4) and alkanes). We combine experimental gas adsorption with GCMC simulations, using generic and adjusted force fields and DFT calculations with the Grimme dispersion correction. By solely adapting the UFF force field to reduce the Lennard-Jones parameter ε, we achieve excellent agreement between the simulated and experimental results not only for ZIF-8 but also for ZIF-20, where the transferability of the adapted force field is successfully tested. Regarding ZIF-8, we show that two different structural configurations are needed to properly describe the adsorption performance of this material, demonstrating that ZIF-8 is undergoing a structural change during gas adsorption. DFT calculations with the Grimme dispersion correction are consistent with the GCMC and experimental observations, illustrating the thermodynamics of the CH(4) adsorption sites and confirming the existence of a new adsorption site with a high binding energy within the 4-ring window of ZIF-8.     

The gomberg-bachmann reaction for the arylation of anilines with aryl diazotates

Simply aqueous sodium hydroxide is sufficient to exclude ionic side reactions and to prepare 2-aminobiphenyls from aryl diazotates and anilines through a new variant of the Gomberg-Bachmann reaction. The metal-free reaction under basic conditions allows to exploit the highly radical-stabilizing effect of the aniline's free amino function for the first time, which leads to a so far unreached regioselectivity.     

Modified Shapiro reactions with bismesitylmagnesium as an efficient base reagent

Bismesitylmagnesium has been shown to successfully mediate the Shapiro reaction. A range of tosylhydrazones has been subjected to the developed system, which furnishes exceptionally high incorporation of the introduced electrophiles and good yields of the functionalized styrenes. At conveniently accessible temperatures and with a comparably small excess of base reagent, this protocol offers an efficient alternative to the lithium-mediated process. Importantly, 1.05 equiv of Weinreb amides are sufficient to obtain aryl enones in good yields.     

Microfluidic chip based nano liquid chromatography coupled to tandem mass spectrometry for the determination of abused drugs and metabolites in human hair

A microfluidic chip based nano-HPLC coupled to tandem mass spectrometry (nano-HPLC-Chip-MS/MS) has been developed for simultaneous measurement of abused drugs and metabolites: cocaine, benzoylecgonine, cocaethylene, norcocaine, morphine, codeine, 6-acetylmorphine, phencyclidine, amphetamine, methamphetamine, MDMA, MDA, MDEA, and methadone in the hair of drug abusers. The microfluidic chip was fabricated by laminating polyimide films and it integrated an enrichment column, an analytical column and a nanospray tip. Drugs were extracted from hairs by sonication, and the chromatographic separation was achieved in 15 min. The drug identification and quantification criteria were fulfilled by the triple quardropule tandem mass spectrometry. The linear regression analysis was calibrated by deuterated internal standards with all of the R ² at least over 0.993. The limit of detection (LOD) and the limit of quantification (LOQ) were from 0.1 to 0.75 and 0.2 to 1.25 pg/mg, respectively. The validation parameters including selectivity, accuracy, precision, stability, and matrix effect were also evaluated here. In conclusion, the developed sample preparation method coupled with the nano-HPLC-Chip-MS/MS method was able to reveal the presence of drugs in hairs from the drug abusers, with the enhanced sensitivity, compared with the conventional HPLC-MS/MS.     

Calix[4]arene-based metal-organic frameworks: towards hierarchically porous materials

An upper rim-functionalised calix[4]arene dicarboxylic acid (H(2)caldc) has been used to prepare four metal-organic frameworks, three of which have been structurally characterised and shown to form two- or three-dimensional network structures. Simulations suggest that such networks are likely to display interesting selectivity to guest molecules.     

Determination of elemental sulfur in phosphorous pentasulfide by temperature modulated differential scanning calorimetry

Phosphorous pentasulfide is an important starting material for a number of commercial chemicals. Examples include lubricant additives (Spikes, Trib Lett 17:469?C489, 2004), agricultural insecticides (Kirk-Othmer, Enycl Chem Technol 14:549?C552, 1995), and mining ore flotation agents. Phosphorous pentasulfide is a mixture of several components, one of which is free elemental sulfur, present at levels of approximately 50?ppm to 20,000?ppm (2?%). The amount of free sulfur present in the phosphorous pentasulfide can impact manufacturing, such as zinc dithiosulfate processing. Therefore, an accurate and fast analytical method to measure elemental sulfur in phosphorous pentasulfide would be of value compared to what is available now.     

The antiproton cell experiment—do antiprotons offer advantages over other particle beam modalities?

The use of heavy charged particles for cancer therapy has the potential for a significant improvement of the therapeutic window compared to standard X-ray treatments. This is due to the improved energy deposition profile, exhibiting a well-defined peak at a depth in target controllable by the initial energy of the beam. Particles heavier than protons in addition show an increase in biological effectiveness. Compared to protons or heavy ions, antiprotons deposit additional annihilation energy, mostly by low energy recoils, resulting in an increase of dose and also adding a component with high biological effectiveness in the target region. The relative magnitude of the physical energy deposition of antiprotons compared to protons was measured at Low Energy Antiproton Ring (LEAR) by A. Sullivan, but no study of the biological effect had been conducted prior to the Antiproton Cell Experiment (AD-4/ACE) experiment at CERN. The special conditions found at CERN present significant challenges, but also offer unique opportunities. 500?ns pulses of antiprotons are extracted from the Antiproton Decelerator (AD) at 500?MeV/c momentum. Biological cell samples are irradiated and clonogenic survival fractions are measured for various doses. To extract biological efficiency, the physical dose deposition is obtained by Monte-Carlo calculations in conjunction with shot-by-shot monitoring of the incoming beam intensity and profile using a silicon pixel detector. Also imaging of the pions resulting from antiproton annihilations in the target using silicon pixel detector technology to determine the actual range in more complex targets with strong variations in material densities was carried out. The feasibility of this technique using a novel arrangement of the detector was demonstrated. This paper describes the ACE experiment and focuses on the different detector activities within the AD-4/ACE collaboration, explaining the experimental set-up, physical and biological methods used, recent results, and future plans.     

Identification of C5Hx isomers in fuel-rich flames by photoionization mass spectrometry and electronic structure calculations

The isomeric composition of C(5)H(x) (x = 2-6, 8) flame species is analyzed for rich flames fueled by allene, propyne, cyclopentene, or benzene. Different isomers are identified by their known ionization energies and/or by comparison of the observed photoionization efficiencies with theoretical simulations based on calculated ionization energies and Franck-Condon factors. The experiments combine flame-sampling molecular-beam mass spectrometry with photoionization by tunable vacuum-UV synchrotron radiation. The theoretical simulations employ the rovibrational properties obtained with B3LYP/6-311++G(d,p) density functional theory and electronic energies obtained from QCISD(T) electronic structure calculations extrapolated to the complete basis set limit. For C(5)H(3), the comparison reveals the presence of both the H(2)CCCCCH (i-C(5)H(3)) and the HCCCHCCH (n-C(5)H(3)) isomer. The simulations also suggest a modest amount of cyclo-CCHCHCCH-, which is consistent with a minor signal for C(5)H(2) that is apparently due to cyclo-CCHCCCH-. For C(5)H(4), contributions from the CH(2)CCCCH(2) (1,2,3,4-pentatetraene), CH(2)CCHCCH, and CH(3)CCCCH (1,3-pentadiyne) isomers are evident, as is some contribution from CHCCH(2)CCH (1,4-pentadiyne) in the cyclopentene and benzene flames. Signal at m/z = 65 originates mainly from the cyclopentadienyl radical. For C(5)H(6), contributions from cyclopentadiene, CH(3)CCCHCH(2), CH(3)CHCHCCH, and CH(2)CHCH(2)CCH are observed. No signal is observed for C(5)H(7) species. Cyclopentene, CH(2)CHCHCHCH(3) (1,3-pentadiene), CH(3)CCCH(2)CH(3) (2-pentyne), and CH(2)CHCH(2)CHCH(2) (1,4-pentadiene) contribute to the signal at m/z = 68. Newly derived ionization energies for i- and n-C(5)H(3) (8.20 +/- 0.05 and 8.31 +/- 0.05 eV, respectively), CH(2)CCHCCH (9.22 +/- 0.05 eV), and CH(2)CHCH(2)CCH (9.95 +/- 0.05 eV) are within the error bars of the QCISD(T) calculations. The combustion chemistry of the observed C(5)H(x) intermediates and the impact on flame chemistry models are discussed.     

Quantitative chirality synchronization in trifluoroethanol dimers

2,2,2-Trifluoroethanol molecules synchronize their transiently chiral gauche configurations upon dimerization in supersonic jet expansions, while they avoid an energetically competitive heteroconfigurational hydrogen bonded dimer topology predicted by extensive quantum chemical calculations.