Enhanced detonation sensitivities of silicon analogs of PETN: reaction force analysis and the role of σ–hole interactions

Si-pentaerythritol tetranitrate (PETN), Si[CH₂ONO₂]₄, is a silicon analog of the widely used explosive PETN, C[CH₂ONO₂]₄. Si-PETN is extremely sensitive to impact, much more so than PETN. This was attributed by Liu et al. to Si-PETN having a much lower activation barrier to decomposition, via a facile rearrangement that is not as readily available to PETN, and which releases considerable energy that can promote further steps. We have investigated computationally why the barrier to the rearrangement is so much lower for Si-PETN than for PETN, using 5, (H₃C)₃C–CH₂ONO₂, and 6, (H₃C)₃Si–CH₂ONO₂, as models for PETN and Si-PETN. Reaction force analysis shows that most of the difference between the rearrangement barriers for 5 and 6 comes about in the initial (reactant) stages of the processes, in which 6 benefits from a 1,3 electrostatic interaction involving a positive σ–hole on the silicon and the negative linking oxygen. The analogous interaction is weaker in 5, since the central carbon does not have positive σ–holes; furthermore, this carbon is less able than silicon to temporarily expand its coordination sphere. A similar explanation involving a positive silicon σ–hole and a linking oxygen is proposed for Si-PETN. The greater exothermicity of the rearrangement of 6 (and also Si-PETN) can be rationalized, following Liu et al., in terms of the formation of the strong Si–O bond.     

Determination of organometallic compounds in surface water and sediment samples with SPME-CGC-ICPMS

Organometal compounds of tin, mercury and lead were simultaneously determined in environmental water and sediment samples by CGC-ICPMS. Instead of classical liquid/liquid extractions, solid phase microextraction was used as sampling technique. In this method, the organometallic compounds arein situ derivatised in the aqueous phase and simultaneously extracted onto a polydimethylsiloxane fiber, so that organic solvents are no longer necessary. The sorbed organometals are subsequently released from the fiber in the GC injection liner by thermal desorption. By sampling from the headspace, only the species of interest are sampled and no interfering matrix components are coextracted. With this new method, derivatisation, extraction, preconcentration and injection into the GC takes only 10 min with a minimum of handling steps. Owing to the very low detection limits (0.13–3.7 ng/1 as metal) only small sample amounts (25 ml of water, 0.5 g of sediment) are needed for one analysis. Finally, SPME is an inexpensive sampling technique that can be used with standard split/splitless injection systems.     

Top-down protein sequencing by CID and ECD using desorption electrospray ionisation (DESI) and high-field FTICR mass spectrometry

We report high resolution spectra for the medium molecular weight proteins myoglobin and cytochrome-c obtained using a custom desorption electrospray ionisation (DESI) source coupled to a Bruker Daltonics 12 T Apex Qe Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). The DESI source was designed for accurate alignment and reproduction of critical geometric variables. A two axis motorised stage was included to enable automated rastering of the sample under the DESI plume. Spectra for the intact proteins have been obtained under single-acquisition conditions and a top-down analysis of cytochrome-c was performed using both collision induced dissociation (CID) and electron capture dissociation (ECD) of the isolated [M+15H]¹⁵⁺ charge state. The sequence coverage is comparable to that obtained using electrospray ionisation, demonstrating the utility of top-down protein analysis by DESI FTICR-MS.     

Regioisomeric analysis of triacylglycerols using silver-ion liquid chromatography-atmospheric pressure chemical ionization mass spectrometry: comparison of five different mass analyzers

Silver-ion high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionization mass spectrometry (APCI-MS) is used for the regioisomeric analysis of triacylglycerols (TGs). Standard mixtures of TG regioisomers are prepared by the randomization reaction from 8 mono-acid TG standards (tripalmitin, tristearin, triarachidin, triolein, trielaidin, trilinolein, trilinolenin and tri-gamma-linolenin). In total, 32 different regioisomeric doublets and 11 triplets are synthesized, separated by silver-ion HPLC using three serial coupled chromatographic columns giving a total length of 75cm. The retention of TGs increases strongly with the double bond (DB) number and slightly for regioisomers having more DBs in sn-1/3 positions. DB positional isomers (linolenic vs. γ-linolenic acids) are also separated and their reverse retention order in two different mobile phases is demonstrated. APCI mass spectra of all separated regioisomers are measured on five different mass spectrometers: single quadrupole LC/MSD (Agilent Technologies), triple quadrupole API 3000 (AB SCIEX), ion trap Esquire 3000 (Bruker Daltonics), quadrupole time-of-flight micrOTOF-Q (Bruker Daltonics) and LTQ Orbitrap XL (Thermo Fisher Scientific). The effect of different types of mass analyzer on the ratio of [M+H-R(i)COOH](+) fragment ions in APCI mass spectra is lower compared to the effect of the number of DBs, their position on the acyl chain and the regiospecific distribution of acyl chains on the glycerol skeleton. Presented data on [M+H-R(i)COOH](+) ratios measured on five different mass analyzers can be used for the direct regioisomeric determination in natural and biological samples.     

Use of a polar ionic liquid as second column for the comprehensive two-dimensional GC separation of PCBs

The orthogonality of three columns coupled in two series was studied for the congener specific comprehensive two-dimensional GC separation of polychlorinated biphenyls (PCBs). A non-polar capillary column coated with poly(5%-phenyl–95%-methyl)siloxane was used as the first (¹D) column in both series. A polar capillary column coated with 70% cyanopropyl-polysilphenylene-siloxane or a capillary column coated with the ionic liquid 1,12-di(tripropylphosphonium)dodecane bis(trifluoromethane-sulfonyl)imide were used as the second (²D) columns. Nine multi-congener standard PCB solutions containing subsets of all native 209 PCBs, a mixture of 209 PCBs as well as Aroclor 1242 and 1260 formulations were used to study the orthogonality of both column series. Retention times of the corresponding PCB congeners on ¹D and ²D columns were used to construct retention time dependences (apex plots) for assessing orthogonality of both columns coupled in series. For a visual assessment of the peak density of PCBs congeners on a retention plane, 2D images were compared. The degree of orthogonality of both column series was, along the visual assessment of distribution of PCBs on the retention plane, evaluated also by Pearson's correlation coefficient, which was found by correlation of retention times t_R,i,2D and t_R,i,1D of corresponding PCB congeners on both column series. It was demonstrated that the apolar + ionic liquid column series is almost orthogonal both for the 2D separation of PCBs present in Aroclor 1242 and 1260 formulations as well as for the separation of all of 209 PCBs. All toxic, dioxin-like PCBs, with the exception of PCB 118 that overlaps with PCB 106, were resolved by the apolar/ionic liquid series while on the apolar/polar column series three toxic PCBs overlapped (105 + 127, 81 + 148 and 118 + 106).