Theoretical aspects of mass spectrometry

The fragmentation patterns of polyatomic ions are the source of the analytical information provided by mass spectrometry. Recent developments in the study of theoretical aspects related to unimolecular dissociations of polyatomic ions have improved our understanding of these processes.     

Synthesis and Characterization of Lead Sulfide Nanoparticles in Zirconia-Silica-Urethane Thin Films Prepared by the Sol-Gel Process

PbS nanocrystals (NCs) ranging between 4–8 nm were incorporated into Zirconium-Silica-Urethane (ZSUR) matrix obtained by the sol-gel method. The sizes of the particles were controlled by temperature treatment and by concentration of PbS in ZSUR matrix. The sizes of PbS NCs were determined by TEM measurements. The quantum size effect could also be extracted from optical absorption and photoluminescence spectra. The new matrix allows incorporation of up to 40% PbS forming a characteristic structure of dendrite by reacting lead acetate with ammonium thiocyanate in sol-gel matrix. The sol precursors of the matrix for Zirconium-Silica-Urethane contained zirconium oxide (ZrO₂) matrix solution, tetramethoxysilane (TMOS), 3-glycid oxypropyl trimethoxysilane (GLYMO) and polyethylene urethane silane (PEUS) synthesized separately. The ZrO₂ matrix solution was obtained from zirconium n-tetrapropoxide in propanol and acetic acid was used as a chelating agent to stabilize the zirconium oxide precursor.     

Kinetic energy release distributions in mass spectrometry

Kinetic energy releases (KERs) in unimolecular fragmentations of singly and multiply charged ions provide information concerning ion structures, reaction energetics and dynamics. This topic is reviewed covering both early and more recent developments. The subtopics discussed are as follows: (1) introduction and historical background; (2) ion dissociation and kinetic energy release: kinematics; potential energy surfaces; (3) the kinetic energy release distribution (KERD); (4) metastable peak observations: measurements on magnetic sector and time-of-flight instruments; energy selected results by photoelectron photoion coincidence (PEPICO); (5) extracting KERDs from metastable peak shapes; (6) ion structure determination and reaction mechanisms: singly and multiply charged ions; biomolecules and fullerenes; (7) theoretical approaches: phase space theory (PST), orbiting transition state (OTS)/PST, finite heat bath theory (FHBT) and the maximum entropy method; (8) exit channel interactions; (9) general trends: time and energy dependences; (10) thermochemistry: organometallic reactions, proton-bound clusters, fullerenes; and (11) the efficiency of phase space sampling.     

Reactions of proton-bound dimers

Thermal reactions of proton-bound dimers, (CH₃CN)₂H ⁺, (CH₃OCH₃)₂H ⁺, and (CH₃COCH₃)₂H⁺, were studied using a selected ion flow tube. Reactions observed include association, switching, and proton transfer. The association channel was observed only for base molecules that had hydrogen bonding protons such as NH₃, CH₃NH₂, (CH₃)₂NH, and CH₃OH. An association-insertion mechaniSoc was proposed in which the central proton of the symmetrically bound dimers is replaced by a protonated base, for example, NH ₄ ⁺ . These reactions are relatively slow, which demonstrates a central barrier along the potential energy surface. Ether-containing dimers do not demonstrate this insertion reaction, except for diethers, for example, CH₃OCH₂CH₂OCH₃, which can form stable bicyclic structures. Dimers such as (HCOOH)₂H⁺, which possess hydrogen bonding protons in the periphery, undergo switching reactions with ammonia and no insertion.     

Radiolabelling of TiO<Subscript>2</Subscript> nanoparticles for radiotracer studies

Industrially manufactured titanium dioxide nanoparticles have been successfully radiolabelled with ⁴⁸V by irradiation with a cyclotron-generated proton beam. Centrifugation tests showed that the ⁴⁸V radiolabels were stably bound within the nanoparticle structure in an aqueous medium, while X-ray diffraction indicated that no major structural modifications to the nanoparticles resulted from the proton irradiation. In vitro tests of the uptake of cold and radiolabelled nanoparticles using the human cell line Calu-3 showed no significant difference in the uptake between both batches of nanoparticles. The uptake was quantified by Inductively Coupled Plasma Mass Spectrometry and high resolution γ-ray spectrometry for cold and radiolabelled nanoparticles, respectively. These preliminary results indicate that alterations to the nanoparticles’ properties introduced by proton bombardment can be controlled to a sufficient extent that their further use as radiotracers for biological investigations can be envisaged and elaborated.     

Dynamic data structures for fat objects and their applications

We present several efficient dynamic data structures for point-enclosure queries, involving convex fat objects in or . Our planar structures are actually fitted for a more general class of objects – (β,δ)-covered objects – which are not necessarily convex, see definition below. These structures are more efficient than alternative known structures, because they exploit the fatness of the objects. We then apply these structures to obtain efficient solutions to two problems: (i) finding a perfect containment matching between a set of points and a set of convex fat objects, and (ii) finding a piercing set for a collection of convex fat objects, whose size is optimal up to some constant factor.