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. 相似文献
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. 相似文献
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. 相似文献
Elemental fluorine substitutes tertiary unactivated hydrogens in an electrophilic mode. This unorthodox substitution depends on the atomic charge density, on the hydrogen atom and on the p-orbital contribution on the CH bond. This is demonstrated by reacting F2 with tertiary CH bonds located on rings of various sizes, producing the corresponding tertiary fluorine derivatives. 相似文献
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, NH4+. 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. 相似文献
Reactions on tertiary hydrogen atoms, attached to unactivated saturated carbons, are very rare and usually inefficient. The electron density however, of a carbon-tertiary hydrogen bond is relatively high and therefore there is a chance it will react with a strong electrophile. One of the strongest electrophiles existing is, of course, the electrophilic fluorine. Two main sources for such an unusual species exist. One source is the various fluoroxy compounds like CF3OF or CF3COOF ant the other is the elemental fluorine itself.Indeed, when fluorine is allowed to react, at low temperatures, with various alkylcyclohexanol esters, a highly regio- and an absolutely stereospecific electrophilic substitution on the tertiary unactivated hydrogen takes place as for example: The radical pathway possibility of these reactions is excluded and it is believed that they are of ionic nature. By dehydrofluorination, a double bond is introduced in sites that no other reagent is known to do, thus activating the molecule towards further chemical transformations. The influence of the electron-withdrawing group on the reaction center will also be discussed.The described reaction is not restricted only to cyclic compounds as aliphatic chains also react as expected, i.e. The scope of these unusual reactions in both alicyclic and aliphatic fields will be evaluated. 相似文献