Optimised Desorption Electrospray Ionisation Mass Spectrometry Imaging (DESI-MSI) for the Analysis of Proteins/Peptides Directly from Tissue Sections on a Travelling Wave Ion Mobility Q-ToF

Desorption electrospray ionisation mass spectrometry imaging (DESI-MSI) is typically known for the ionisation of small molecules such as lipids and metabolites, in singly charged form. Here we present a method that allows the direct detection of proteins and peptides in multiply charged forms directly from tissue sections by DESI. Utilising a heated mass spectrometer inlet capillary, combined with ion mobility separation (IMS), the conditions with regard to solvent composition, nebulising gas flow, and solvent flow rate have been explored and optimised. Without the use of ion mobility separation prior to mass spectrometry analysis, only the most abundant charge series were observed. In addition to the dominant haemoglobin subunit(s) related trend line in the m/z vs drift time (DT) 2D plot, trend lines were found relating to background solvent peaks, residual lipids and, more importantly, small proteins/large peptides of lower abundance. These small proteins/peptides were observed with charge states from 1+ to 12+, the majority of which could only be resolved from the background when using IMS. By extracting charge series from the 2D m/z vs DT plot, a number of proteins could be tentatively assigned by accurate mass. Tissue images were acquired with a pixel size of 150 μm showing a marked improvement in protein image resolution compared to other liquid-based ambient imaging techniques such as liquid extraction surface analysis (LESA) and continuous-flow liquid microjunction surface sampling probe (LMJ-SSP) imaging.

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Preparation and Properties of Elastomer Composites Containing “Graphene”-Based Fillers: A Review

Elastomers are materials showing exceptional elasticity and are used for numerous applications. However, their low stiffness as well as their insulating behavior can be limiting so the incorporation of graphene-based materials can help and improve drastically their properties. With high Young's modulus, high electrical and thermal conductivities, graphene and graphene-like fillers seem ideal fillers to effectively tune elastomers properties. With low graphene-like loadings, most elasticity properties of elastomers could be preserved while increasing or adding new properties to the composites to enable new applications. Herein, we focus on the effects of “graphene” incorporation into elastomers and we will highlight the key parameters to effectively monitor the changes.     

Acid-Catalyzed Rearrangements of 5,6-exo-Epoxy-7-oxabicyclo[2.2.1]hept-2-yl Derivatives. Migratory Aptitudes of Acyl vs. Alkyl Groups in Wagner-Meerwein Transpositions

In the presence of HSO₃F/Ac₂O in CH₂CL₂, 2-exo- and 2-endo-cyano-5,6-exo-epoxy-7-oxabicyclo[2.2.1]hept-2-yl acetates ( 6a , b ) gave products derived from the epoxide-ring opening and a 1,2-shift of the unsubstituted alkyl group (σ bond C(3)–C(4)). In contrast, under similar conditions, the 5,6-exo-epoxy-7-oxabicyclo[2.2.1]heptan-2-one ( 6c ) gave 5-oxo-2-oxabicyclo[2.2.1]heptane-3,7-diyl diacetates 20 and 21 arising from the 1,2-shift of the acyl group. Acid treatment of 5,6-exo-epoxy-2,2-dimethoxy-7-oxabicyclo[2.2.1]heptane ( 6d ) and of 5,6-exo-epoxy-2,2-bis(benzyloxy)-7-oxabicyclo[2.2.1]heptane ( 6e ) gave minor products arising from epoxide-ring opening and the 1,2-shift of σ bond C(3)–C(4) and major products ( 25 , 29 ) arising from the 1,3-shift of a methoxy and benzyloxy group, respectively. Under similar conditions, 5,6-exo-epoxy-2,2-ethylenedioxy-7-oxabicyclo[2.2.1]heptane ( 6f ) gave 1,1-(ethylenedioxy)-2-(2-furyl)ethyl acetate ( 32 , major) and a minor product 33 , arising from the 1,2-shift of σ bond C(3)–C(4). The following order of migratory aptitudes for 1,2-shifts toward electron-deficient centers has been established: acyl > alkyl > alkyl α-substituted with inductive electron-withdrawing groups. This order is valid for competitive Wagner-Meerwein rearrangements involving equilibria between carbocation intermediates with similar exothermicities.     

Synthesis and polymerization of racemic and optically active β-substituted β-propiolactones. II: β-monosubstituted and β-disubstituted monomers and polymers with different optical purities

β-(trichloromethyl)-β-propiolactone (CCl₃-PL), β-(trifluoromethyl,methyl)-β-propiolactone (CF₃, Me-PL) and β-(trifluoromethyl,ethyl)-β-propiolactone (CF₃,Et-PL) have been obtained by the reaction of ketene with chloral, 1,1,1-trifluoroacetone and 1,1,1-trifluorobutanone, respectively. Chiral catalysis lead to optically active monomers. The enantiomeric excess of the lactones has been measured by ¹H-NMR spectroscopy, in the presence of 2,2,2-trifluoro-1-(9-anthryl)ethanol or an europium chiral shift reagent. Polymerizations have been carried out in bulk or in toluene, at 60°C or 80°C, using mainly organometallic initiators. The Polymers become insoluble and crystalline at enantiomeric excesses over 80% for CCl₃-PL and 70% for CF₃,Me-PL. Melting temperatures were recorded from 238 to 268°C for poly(CCl₃-PL) and from 78 to 100°C for poly(CF₃,Me-PL), depending upon the molecular weight and the enantiomeric excess. The ¹³C-NMR specroscopy of poly(CCL₃-PL) indicates that the polymerization of the corresponding lactone leads to polymers of increasing degrees of isotacticity with the enantiomeric excess of the monomer.     

3,5-Bis(ethynyl)pyridine and 2,6-bis(ethynyl)pyridine spanning two Fe(Cp*)(dppe) units: role of the nitrogen atom on the electronic and magnetic couplings

The role of the nitrogen atom on the electronic and magnetic couplings of the mono-oxidized and bi-oxidized pyridine-containing complex models [2,6-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) and [3,5-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) is theoretically tackled with the aid of density-functional theory (DFT) and multireference configuration interaction (MR-CI) calculations. Results are analyzed and compared to those obtained for the reference complex [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+). The mono-oxidized species show an interesting behavior at the borderline between spin localization and delocalization and one through-bond communication path among the two involving the central ring, is favored. Investigation of the spin state of the dicationic complexes indicates ferromagnetic coupling, which can differ in magnitude from one complex to the other. Very importantly, electronic and magnetic properties of these species strongly depend not only upon the location of the nitrogen atom in the ring versus that of the organometallic end-groups but also upon the architectural arrangement of one terminus, with respect to the other and/or vis-à-vis the central ring. To help validate the theoretical results, the related families of compounds [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+), [2,6-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+), [3,5-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+) (n = 0-2) were experimentally synthesized and characterized. Electrochemical, spectroscopic (infrared (IR), M?ssbauer), electronic (near-infrared (NIR)), and magnetic properties (electron paramagnetic resonance (EPR), superconducting quantum interference device (SQUID)) are discussed and interpreted in the light of the theoretical data. The set of data obtained allows for many strong conclusions to be drawn. A N atom in the long branch increases the ferromagnetic interaction between the two Fe(III) spin carriers (J > 500 cm(-1)), whereas, when placed in the short branch, it dramatically reduces the magnetic exchange in the di-oxidized species (J = 2.14(5) cm(-1)). In the mixed-valence compounds, when the N atom is positioned on the long branch, the intermediate excited state is higher in energy than the different ground-state conformers and the relaxation process provides exclusively the Fe(II)/Fe(III) localized system (H(ab) ≠ 0). Positioning the N atom on the short branch modifies the energy profile and the diabatic mediating state lies just above the reactant and product diabatic states. Consequently, the LMCT transition becomes less energetic than the MMCT transition. Here, the direct coupling does not occur (H(ab) = 0) and only the coupling through the bridge (c) and the reactant (a) and product (b) diabatic states is operating (H(ac) = H(bc) ≠ 0).     

Capture of the complex [Ni(dto)2]2- (dto2- = dithiooxalato ligand) in a Mo12 ring: synthesis, characterizations, and application toward the reduction of protons

The encapsulation of the complex [Ni(dto)(2)](2-) within an oxothiododecamolybdic cyclic cluster has been investigated. The resulting molybdenum ring, [Mo(12)O(12)S(12)(OH)(12)(Ni(dto)(2))](2-), corresponds to the first example of the {Mo(2)O(2)S(2)}-based assembly arranged around a 3d transition-metal complex. It was unambiguously characterized in the solid state and in solution by FT-IR spectroscopy, single-crystal X-ray diffraction, NMR, UV-visible spectroscopy, and electrospray ionization-high-resolution mass spectrometry (ESI-HRMS). The latter technique revealed to be a powerful tool for the characterization of templated molybdenum ring systems in solution and gave excellent results in high resolution. The electronic spectrum of [Mo(12)O(12)S(12)(OH)(12)(Ni(dto)(2))](2-) evidenced a strong red shift of the LMCT bands attributed to the complex [Ni(dto)(2)](2-), suggesting significant variations of the electronic properties upon its encapsulation within the Mo(12) ring. These differences were demonstrated by electrochemical studies in CH(3)CN, which also revealed, for both compounds [Ni(dto)(2)](2-) and [Mo(12)O(12)S(12)(OH)(12)(Ni(dto)(2))](2-), electrocatalytic properties for the reduction of protons. These results evidence the ability of dithioxalato complexes to act as electrocatalysts for the hydrogen evolution reaction (HER) and confirm such a property for oxothiomolybdenum rings.     

Use of 73Ge NMR spectroscopy for the study of electronic interactions

The lack of understanding of the structural and electronic factors that affect the often difficult to observe germanium resonance has been a major deterrent to studies of bonding interactions at germanium. We utilized the symmetrical system GeR 4 to determine what structural factors inherent in the R group affect the shape and position of the (73)Ge resonance. The (73)Ge resonances of symmetrical tetrakis germanium compounds of the type GeR 4 (R = alkyl, aryl), GeX 4 (X = F, Cl, Br, I), Ge(OR) 4 (R = alkyl, methoxyalkyl, dimethylaminoalkyl), Ge(NR 2) 4 (R = alkyl), and Ge(SR) 4 (R = alkyl, dimethylaminoalkyl) were examined for evidence of intramolecular coordination. Although many of these compounds have sharp resonances due to idealized tetrahedral symmetry with relatively long relaxation times, others have broad or no observable resonances due to fast quadrupolar relaxation. We hypothesize that the perturbation of symmetry by even weak Lewis interactions or conformational changes causes broadening of the resonance before the interaction can become sufficiently strong to cause the significant low-frequency shift generally associated with hypercoordination in most nuclei. Intermolecular coordination to GeCl 4 is believed to be responsible for the low-frequency shifts in (73)Ge resonances and the associated changes in peak widths in mixtures with bases such as tributylphosphine oxide (TBPO) and triethylphosphine oxide (TEPO). Adduct formation with these bases is confirmed by broad (31)P resonances that are resolved into five peaks at -40 degrees C. The exchange-broadened resonances due to the 1:1 and 1:2 TEPO adducts are also observed at -40 degrees C in the (73)Ge spectrum. Thus, relatively strong bonding to the germanium in GeCl 4 results in both low-frequency shifts and broadening of the resonance. The broad (73)Ge resonances that occur in some compounds may be in part due to exchange as well as quadrupolar relaxation.