Characterization of Electron Transfer Dissociation in the Orbitrap Velos HCD Cell

Electron transfer dissociation (ETD) is commonly employed in ion traps utilizing rf fields that facilitate efficient electron transfer reactions. Here, we explore performing ETD in the HCD collision cell on an Orbitrap Velos instrument by applying a static DC gradient axially to the rods. This gradient enables simultaneous three dimensional, charge sign independent, trapping of cations and anions, initiating electron transfer reactions in the center of the HCD cell where oppositely charged ions clouds overlap. Here, we evaluate this mode of operation for a number of tryptic peptide populations and the top-down sequence analysis of ubiquitin. Our preliminary data show that performing ETD in the HCD cell provides similar fragmentation as ion trap-ETD but requires further optimization to match performance of ion trap-ETD.      

Effect of cucurbit[n]urils on tropicamide and potential application in ocular drug delivery

The supramolecular interactions of the ocular drug tropicamide (TR) with cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) were investigated in aqueous solutions by using ¹H NMR, ESI-MS and UV–vis spectroscopic techniques. The results indicate a 1:1 binding stoichiometry of TR with CB7 and CB8. The binding constants of TR in its protonated form were higher (e.g. K = 4 × 10⁶ M^? 1 with CB8) than in its neutral form (e.g. K = 1.4 × 10⁴ M^? 1 with CB8), which led to a complexation-induced increase in its pK _a value of ca. 0.5 and 2 units with CB7 and CB8, respectively. In the presence of about 1% (w/v) CB8, the ionisation degree of 0.1% (w/v) TR was increased from 2% to 62% at neutral pH. The increase in the pK _a value and thus stabilisation of the protonated TR species at neutral pH is discussed in the context of supramolecular drug delivery of ophthalmologic drugs.     

Voltammetry coupled to mass spectrometry in the presence of isotope O labeled water for the prediction of oxidative transformation pathways of activated aromatic ethers: Acebutolol

The coupling between an electrochemical cell (EC) and a mass spectrometer (MS) is a useful screening tool (EC-MS) to study the oxidative transformation pathways of various electroactive species. For that purpose, we showed that the EC-MS method, carried out in the presence and absence of isotope ¹⁸O labeled water leads not only to a fast identification of oxidation products but also leads to a fast elucidation of the mechanism pathway reaction. We examined herein the case of the electrochemical hydrolysis of activated aromatic ether. Acebutolol (β-blockers) was selected herein as model of activated aromatic ether, and its electrochemical oxidation was examined in both the presence and absence of isotope ¹⁸O labeled water. To elucidate electrochemical hydrolysis pathway reaction: O-dealkylation or O-dealkoxylation, our approach was used to prove its applicability. The electrochemical oxidation mechanism was then elucidated showing an O-dealkoxylation reaction. In addition, density functional theory (DFT) calculations fully support the experimental conclusions.     

Efficient One‐Pot Four‐Component Synthesis and X‐ray Crystallographic Structure of 2‐Pyridone Derivatives

A series of 3‐cyano‐2‐pyridone derivatives were synthesized by one‐pot four‐component condensation reaction involving a benzaldehyde derivative, alkyl cyanoacetate, acyclic or cyclic ketones, and ammonium acetate in reflux condition. The X‐ray structure of the products 5a and 5d confirm symmetric dimers via hydrogen bonding interactions between individual pyridine molecules showing, in addition, also π–π stacking interactions.     

Immunomagnetic nanoparticle based quantitative PCR for rapid detection of Salmonella

We have developed a rapid and sensitive method for immunomagnetic separation (IMS) of Salmonella along with their real time detection via PCR. Silica-coated magnetic nanoparticles were functionalized with carboxy groups to which anti-Salmonella antibody raised against heat-inactivated whole cells of Salmonella were covalently attached. The immuno-captured target cells were detected in beverages like milk and lemon juice by multiplex PCR and real time PCR with a detection limit of 10⁴ cfu.mL^?1 and 10³ cfu.mL^?1, respectively. We demonstrate that IMS can be used for selective concentration of target bacteria from beverages for subsequent use in PCR detection. PCR also enables differentiation of Salmonella typhi and Salmonella paratyphi A using a set of four specific primers. In addition, IMS—PCR can be used as a screening tool in the food and beverage industry for the detection of Salmonella within 3–4 h which compares favorably to the time of several days that is needed in case of conventional detection based on culture and biochemical methods.

Efficient Method for Oxidation of Ketones to Esters with 4-Aminoperoxybenzoic Acid Supported On Silica Gel

4-Aminoperoxybenzoic acid supported on silica gel was found to be a versatile and efficient oxidant for the oxidation of ketones to esters.     

Building block synthesis of predominantly (E) symmetrical and unsymmetrical 1,2-difluorostilbenes from 1,2-dibromo-1,2-difluoroethene

An efficient synthesis of predominantly (E) symmetrical or unsymmetrical 1,2-difluorostilbenes based on the Suzuki–Miyaura palladium-catalyzed cross-coupling reaction of arylboronic acids with predominantly (E)-1,2-dibromo-1,2-difluoroethene in the presence of Cs₂CO₃ in toluene is described. The reaction preserved the stereochemistry of the building block and performed in good yield independently of the electron-withdrawing or electron-donating character of the substituents.     

Structure and Polymorphism of M(thd)3 (M = Al,Cr, Mn,Fe, Co,Ga, and In)

Formation, crystal structure, polymorphism, and transition between polymorphs are reported for M(thd)₃, (M = Al, Cr, Mn, Fe, Co, Ga, and In) [(thd)^– = anion of H(thd) = C₁₁H₂₀O₂ = 2, 2, 6, 6‐tetramethylheptane‐3, 5‐dione]. Fresh crystal‐structure data are provided for monoclinic polymorphs of Al(thd)₃, Ga(thd)₃, and In(thd)₃. Apart from adjustment of the M–O_k bond length, the structural characteristics of M(thd)₃ complexes remain essentially unaffected by change of M. Analysis of the M–O_k, O_k–C_k, and C_k–C_k distances support the notion that the M–O_k–C_k–C_k–C_k–O_k– ring forms a heterocyclic unit with σ and π contributions to the bonds. Tentative assessments according to the bond‐valence or bond‐order scheme suggest that the strengths of the σ bonds are approximately equal for the M–O_k, O_k–C_k, and C_k–C_k bonds, whereas the π component of the M–O_k bonds is small compared with those for the O_k–C_k, and C_k–C_k bonds. The contours of a pattern for the occurrence of M(thd)₃ polymorphs suggest that polymorphs with structures of orthorhombic or higher symmetry are favored on crystallization from the vapor phase (viz. sublimation). Monoclinic polymorphs prefer crystallization from solution at temperatures closer to ambient. Each of the M(thd)₃ complexes subject to this study exhibits three or more polymorphs (further variants are likely to emerge consequent on systematic exploration of the crystallization conditions). High‐temperature powder X‐ray diffraction shows that the monoclinic polymorphs convert irreversibly to the corresponding rotational disordered orthorhombic variant above some 100–150 °C (depending on M). The orthorhombic variant is in turn transformed into polymorphs of tetragonal and cubic symmetry before entering the molten state. These findings are discussed in light of the current conceptions of rotational disorder in molecular crystals.     

Finding optimal finite field strengths allowing for a maximum of precision in the calculation of polarizabilities and hyperpolarizabilities

The finite field method, widely used for the calculation of static dipole polarizabilities or the first and second hyperpolarizabilities of molecules and polymers, is thoroughly explored. The application of different field strengths and the impact on the precision of the calculations were investigated. Borders could be defined and characterized, establishing a range of feasible field strengths that guarantee reliable numerical results. The quality of different types of meshes to screen the feasible region is assessed. Extrapolation schemes are presented that reduce the truncation error and allow to increase the precision of finite field calculations by one to three orders of magnitude. © 2013 Wiley Periodicals, Inc.