Aliphatic Cations Research Articles

Polyamine Catabolism Is Enhanced after Traumatic Brain Injury

Polyamines spermine and spermidine are highly regulated, ubiquitous aliphatic cations that maintain DNA structure and function as immunomodulators and as antioxidants. Polyamine homeostasis is disrupted after brain injuries, with concomitant generation of toxic metabolites that may contribute to secondary injuries. To test the hypothesis of increased brain polyamine catabolism after traumatic brain injury (TBI), we determined changes in catabolic enzymes and polyamine levels in the rat brain after lateral controlled cortical impact TBI. Spermine oxidase (SMO) catalyzes the degradation of spermine to spermidine, generating H2O2 and aminoaldehydes. Spermidine/spermine-N(1)-acetyltransferase (SSAT) catalyzes acetylation of these polyamines, and both are further oxidized in a reaction that generates putrescine, H2O2, and aminoaldehydes. In a rat cortical impact model of TBI, SSAT mRNA increased subacutely (6-24 h) after TBI in ipsilateral cortex and hippocampus. SMO mRNA levels were elevated late, from 3 to 7 days post-injury. Polyamine catabolism increased as well. Spermine levels were normal at 6 h and decreased slightly at 24 h, but were normal again by 72 h post-injury. Spermidine levels also decreased slightly (6-24 h), then increased by approximately 50% at 72 h post-injury. By contrast, normally low putrescine levels increased up to sixfold (6-72 h) after TBI. Moreover, N-acetylspermidine (but not N-acetylspermine) was detectable (24-72 h) near the site of injury, consistent with increased SSAT activity. None of these changes were seen in the contralateral hemisphere. Immunohistochemical confirmation indicated that SSAT and SMO were expressed throughout the brain. SSAT-immunoreactivity (SSAT-ir) increased in both neuronal and nonneuronal (likely glial) populations ipsilateral to injury. Interestingly, bilateral increases in cortical SSAT-ir neurons occurred at 72 h post-injury, whereas hippocampal changes occurred only ipsilaterally. Prolonged increases in brain polyamine catabolism are the likely cause of loss of homeostasis in this pathway. The potential for simple therapeutic interventions (e.g., polyamine supplementation or inhibition of polyamine oxidation) is an exciting implication of these studies.

Complexes ofThermotoga maritimaS-adenosylmethionine decarboxylase provide insights into substrate specificity

The polyamines putrescine, spermidine and spermine are ubiquitous aliphatic cations and are essential for cellular growth and differentiation. S-Adenosylmethionine decarboxylase (AdoMetDC) is a critical pyruvoyl-dependent enzyme in the polyamine-biosynthetic pathway. The crystal structures of AdoMetDC from humans and plants and of the AdoMetDC proenzyme from Thermotoga maritima have been obtained previously. Here, the crystal structures of activated T. maritima AdoMetDC (TmAdoMetDC) and of its complexes with S-adenosylmethionine methyl ester and 5'-deoxy-5'-dimethylthioadenosine are reported. The results demonstrate for the first time that TmAdoMetDC autoprocesses without the need for additional factors and that the enzyme contains two complete active sites, both of which use residues from both chains of the homodimer. The complexes provide insights into the substrate specificity and ligand binding of AdoMetDC in prokaryotes. The conservation of the ligand-binding mode and the active-site residues between human and T. maritima AdoMetDC provides insight into the evolution of AdoMetDC.

Structure−Properties Relationships of Lithium Electrolytes Based on Ionic Liquid

Low-melting ionic liquid, IL, based on small aliphatic quaternary ammonium cations ([R(1)R(2)R(3)NR](+), where R(1), R(2), R(3) = CH(3) or C(2)H(5), R = C(3)H(7), C(4)H(9), C(6)H(13), C(8)H(17), CF(3)C(3)H(6)) and imide anion were prepared and characterized. The physicochemical and electrochemical properties of these ILs, including melting point, glass transition, and degradation temperatures; viscosity; density; ionic conductivity; diffusion coefficient; and electrochemical stability, were determined. Heteronuclear Overhauser NMR spectroscopy experiments were also performed to point out the presence of pair correlation between the different moieties. The LiTFSI addition effect on the IL properties was studied with the same methodology. Some nanoscale organization with segregation of polar and apolar domains was observed. ILs with small alkyl chain length or fluorinated ammonium exhibit very high electrochemical stability in oxidation.

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Asymmetrical dicationic ionic liquids based on both imidazolium and aliphatic ammonium as potential electrolyte additives applied to lithium secondary batteries

Asymmetrical dicationic ionic liquids based on the combination of imidazolium and aliphatic ammonium cations with TFSI anion, MIC n N 111-TFSI 2, have been synthesized for the first time, wherein MI represents imidazolium cation, N 111 represents trimethylammonium cation, and C n represents spacer length. The physical and electrochemical properties of this family of ionic liquids were studied. 1-(3-Methylimidazolium-1-yl)ethane-(trimethylammonium) bi[bis(trifluoromethane-sulfonyl) imide] (MIC 2N 111-TFSI 2) shows solid–solid transition characteristics. 1-(3-Methylimidazolium-1-yl)pentane-(trimethylammonium) bi[bis(trifluoromethan-esulfonyl)imide] (MIC 5N 111-TFSI 2) has one of the lowest solid–liquid transformation temperatures among analogues, and belongs to the greatest thermal stable ionic liquids. Additionally, it has an order of conductivity of 10 −1 ms cm −1, and electrochemical window of about 3.7 V at room temperature. To evaluate the potential of MIC 5N 111-TFSI 2 as an additive of electrolyte for lithium secondary batteries, cells composed of LiMn 2O 4 cathode/1 M LiPF 6 in EC:DMC (1:1, v/v) electrolytic solution containing 5 wt% of MIC 5N 111-TFSI 2/lithium metal anode have been prepared. The charge–discharge cycling test reveals that unlike the cases of Li/LiMn 2O 4 cells employing a conventional electrolyte with a monocationic ionic liquid, such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EtMeImTFSI) as an additive, the performances of Li/LiMn 2O 4 cells do not drop with the addition of MIC 5N 111-TFSI 2 at 1 C rate, moreover, the cell exhibits better discharge capacity and cycle durability compared with the cell using the conventional electrolyte.

The possible roles for polyamines in the initiation process of SV40 DNA replication in vitro

The polyamines are aliphatic cations which are present in millimolar concentrations in all mammalian cells, and are required for optimal growth of almost all cell types. In this study, the roles of polyamines in DNA replication in vitro and the mechanism by which polyamines affected DNA replication were examined using simian virus 40 DNA replication system in vitro. We found that polyamines inhibited DNA replication, but it is not clear at which stage this occurs. Spermidine inhibited the DNA cleavage by topoisomerase I at 8.0 mM, but stimulated its activity at 1.0 mM. Spermine also inhibited its activity at 4.0 mM, but stimulated at 1.0 mM. The ssDNA binding activity of replication protein A was slightly affected by polyamines. Polyamines, especially spermine, also significantly reduced polymerase alpha-primase activity at 133 microM. Taken together, we suggest that the major inhibition of SV40 DNA replication may be due to the inhibition of pol alpha-primase activity, and possible roles for polyamines in the initiation process are discussed.

The influence of modification on structural, textural and adsorption properties of bentonite

Natural bentonite clay from the Bogovina locality in Serbia was Na-exchanged and modified using hexadecyll-trimethylammonium bromide as surfactant and organobentonite was obtained. The influence of modifications on the structural, textural and sorption properties of bentonite was investigated. It was estimated that modifications solely replace exchangeable cations in smectite layers, whereas other admixture minerals (quartz, calcite, feldspar) in bentonite remain unaffected. According to X-ray results the modification lead to changes in the smectite structure by either decreasing, for Na-bentonite, or increasing, for organobentonite, the interplanar spacing, JQOI- The appearance of three new bands in IR spectra of HDTMA-bentonite comparing to those of raw and Na-bentonite assigned to the methylene vibrations confirmed the embedding of aliphatic cations into smectite structure. In organobentonite a significant change in textural properties was observed. In particular, specific surface area dramatically decreased while originally meso and microporous material became almost completely non-porous. Despite almost insignificant specific surface area the synthesized organobentonite due to gained organophyllity of its surface exhibits exquisite adsorption properties toward investigated textile dyes having adsorption capacity approx. 2 times higher than activated carbon.

Transition state ring sizes in H-transfers in closed shell aliphatic cations

We use theory to determine the relative rates of 4-, 5- and 6-membered ring H-transfers in closed shell cations, a comparison not possible experimentally due to interference from competing processes. H-transfers of increasing ring size were characterized by ab initio, density functional and/or RRKM studies of CH 3N +H CH 2, NH 2CH N +HCH 3, NH 2CH 2N +H CH 2, NH 2CH 2CH 2N +H CH 2, N +H 2 CHCH 2NHCH 3 and CH 3NHCH 2NH + CH 2. The critical energies for these reactions decreased and the rates thereof increased dramatically with increasing H-transfer ring size. Transition state ring strain and avoiding orbital symmetry constraints together produce the same sequence of reaction rates (6 > 5 > 4 membered ring preference) and critical energies (4 > 5 > 6 membered ring order) in open and closed shell organic cations. Twisting around double bonds during H-transfers breaks conjugation and allows the reactions to bypass orbital symmetry constraints.

Electrochemical Aspects of Asymmetric Phosphonium Ionic Liquids

Asymmetric aliphatic tetraalkyl phosphonium cations form room-temperature ionic liquids with iodide as an anion. Isobutyl-trihexyl phosphonium iodide shows the highest ionic conductivity at room temperature and it is enhanced by 3-methoxypropionitrile addition. A cyclovoltammetric study shows adequate redox behavior for nanocrystalline solar cells devices.

Tumor Necrosis Factor α Induces Spermidine/Spermine N1-Acetyltransferase through Nuclear Factor κBin Non-small Cell Lung Cancer Cells

Tumor necrosis factor alpha (TNFalpha) is a potent pleiotropic cytokine produced by many cells in response to inflammatory stress. The molecular mechanisms responsible for the multiple biological activities of TNFalpha are due to its ability to activate multiple signal transduction pathways, including nuclear factor kappaB (NFkappaB), which plays critical roles in cell proliferation and survival. TNFalpha displays both apoptotic and antiapoptotic properties, depending on the nature of the stimulus and the activation status of certain signaling pathways. Here we show that TNFalpha can lead to the induction of NFkappaB signaling with a concomitant increase in spermidine/spermine N(1)-acetyltransferase (SSAT) expression in A549 and H157 non-small cell lung cancer cells. Induction of SSAT, a stress-inducible gene that encodes a rate-limiting polyamine catabolic enzyme, leads to lower intracellular polyamine contents and has been associated with decreased cell growth and increased apoptosis. Stable overexpression of a mutant, dominant negative IkappaBalpha protein led to the suppression of SSAT induction by TNFalpha in these cells, thereby substantiating a role of NFkappaB in the induction of SSAT by TNFalpha. SSAT promoter deletion constructs led to the identification of three potential NFkappaB response elements in the SSAT gene. Electromobility shift assays, chromatin immunoprecipitation experiments and mutational studies confirmed that two of the three NFkappaB response elements play an important role in the regulation of SSAT in response to TNFalpha. The results of these studies indicate that a common mediator of inflammation can lead to the induction of SSAT expression by activating the NFkappaB signaling pathway in non-small cell lung cancer cells.

Levels of polyamines and kinetic characterization of their uptake in the soybean pathogen Phytophthora sojae.

Polyamines are ubiquitous biologically active aliphatic cations that are at least transiently available in the soil from decaying organic matter. Our objectives in this study were to characterize polyamine uptake kinetics in Phytophthora sojae zoospores and to quantify endogenous polyamines in hyphae, zoospores, and soybean roots. Zoospores contained 10 times more free putrescine than spermidine, while hyphae contained only 4 times as much free putrescine as spermidine. Zoospores contained no conjugated putrescine, but conjugated spermidine was present. Hyphae contained both conjugated putrescine and spermidine at levels comparable to the hyphal free putrescine and spermidine levels. In soybean roots, cadaverine was the most abundant polyamine, but only putrescine efflux was detected. The selective efflux of putrescine suggests that the regulation of polyamine availability is part of the overall plant strategy to influence microbial growth in the rhizosphere. In zoospores, uptake experiments with [1,4-(14)C]putrescine and [1,4-(14)C]spermidine confirmed the existence of high-affinity polyamine transport for both polyamines. Putrescine uptake was reduced by high levels of exogenous spermidine, but spermidine uptake was not reduced by exogenous putrescine. These observations suggest that P. sojae zoospores express at least two high-affinity polyamine transporters, one that is spermidine specific and a second that is putrescine specific or putrescine preferential. Disruption of polyamine uptake or metabolism has major effects on a wide range of cellular activities in other organisms and has been proposed as a potential control strategy for Phytophthora. Inhibition of polyamine uptake may be a means of reducing the fitness of the zoospore along with subsequent developmental stages that precede infection.

Kinetic Energy Release in the Loss of Water from n-Propanol Cation

Unimolecular dissociations of ionized aliphatic alcohols have been investigated extensively. Interestingly, competition between loss of hydrogen atom and water is quite different for lower aliphatic alcohol cations with different chain lengths. Loss of H dominates in the dissociations of methanol and ethanol cations, while loss of H2O does in those of n-propanol and n-butanol cations. Theoretical studies agree that a H atom of the methyl group migrates to the O atom of the hydroxyl group prior to loss of H2O from these alcohol ions. In a recent computational study, the energy barriers for the H migration in the H2O loss were compared. The barrier decreases as the aliphatic chain increases. Very recently, we proposed a potential energy surface (PES) for the loss of H2O and H from n-propanol ion by density functional theory (DFT) molecular orbital calculations. Initially CH3CH2CH2OH +• isomerizes to CH2CH2CH2OH2 + via a five centered transition state (1,4-H shift). This is the rat-determining step in the H2O loss. CH2CH2CH2OH2 + undergoes further isomerizations to ion-dipole complexes, c-C3H6 •••H2O prior to loss of H2O. Based on the obtained PES, the experimental results of the metastable dissociation such as the branching ratio and the isotopic effect on the H loss could be well interpreted by the statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The kinetic energy release (KER), however, has not been investigated in detail, which provides valuable information on the exit channel in dissociation. In this work, the KER distribution (KERD) in the H2O loss from metastable npropanol cation has been investigated using mass-analyzed ion kinetic energy (MIKE) spectrometry. The nature of the dissociation is discussed by comparing the experimental result with statistical phase space theory (PST) calculations.

Intramolecular Hydrogen Bonding and Hydrogen Atom Abstraction in Gas-Phase Aliphatic Amine Radical Cations

The intramolecular hydrogen atom abstraction by the nitrogen atom in isolated aliphatic amine radical cations is examined experimentally and with composite high-level ab initio methods of the G3 family. The magnitude of the enthalpy barriers toward H-atom transfer varies with the shape and size of the cyclic transition state and with the degree of substitution at the nitrogen and carbon atoms involved. The lower barriers are found for 1,5- and 1,6-abstraction, for chairlike transition states, for abstraction reactions in ionized primary amines, and for abstraction of H from tertiary carbon atoms. In most cases, the internal energy required for 1,4-, 1,5-, and 1,6-hydrogen atom abstraction to occur is less than that required for gas-phase fragmentation by simple cleavage of C-C bonds, which explains why H-atom transfer can be reversible and result in extensive H/D exchange prior to the fragmentation of many low-energy deuterium labeled ionized amines. The H-atom transfer to nitrogen is exothermic for primary amine radical cations and endothermic for tertiary amines. It gives rise to a variety of distonic radical cations, and these may undergo further isomerization. The heat of formation of the gauche conformers of the gamma-, delta-, and epsilon-distonic isomers is up to 25 kJ mol(-1) lower than that of the corresponding trans forms, which is taken to reflect C-H-N hydrogen bonding between the protonated amino group and the alkyl radical site.

Preparation of room temperature ionic liquids based on aliphatic onium cations and asymmetric amide anions and their electrochemical properties as a lithium battery electrolyte

The physical and electrochemical properties of room temperature ionic liquids (RTILs) based on asymmetric amide anions (TSAC: 2,2,2-trifluoro- N-(trifluoromethylsulfonyl)acetamide, C1C2: N-(trifluoromethylsulfonyl)pentafluoroethylsulfonamide) and aliphatic onium cations, such as ammonium, phosphonium, and sulfonium, were reported. The melting point of the C1C2 salts decreased compared to the corresponding TFSI salts (TFSI: bis(trifluoromethylsulfonyl)imide), however, the viscosity was about twice that of the TFSI salts. Relatively low viscosity RTILs based on aliphatic onium cations could be prepared using the TSAC anion and tetraalkylammonium cation containing an alkoxy group. The linear sweep voltammogram of these RTILs with and without Li-TFSI were investigated in order to estimate the electrochemical windows and possible use as a lithium battery electrolyte.

Competing Simple Cleavage Reactions: The Elimination of Alkyl Radicals from Amine Radical Cations

Two different alkyl radicals can be expelled when unsymmetrical aliphatic amine radical cations undergo C-C bond cleavage. The branching ratio is strongly dependent on the internal energy of the reactant, even when the competition involves loss of closely related alkyl radicals. In mass spectrometers, the rate of loss of the smaller radical (excepting methyl) always exceeds the rate of loss of the larger close to threshold. The preference is reversed for the more highly energized ions that react in the ion source, demonstrating that the rate of loss of the larger radical rises much more rapidly with increasing internal energy than does the rate of loss of the smaller radical. This result is not easily reconciled with a simple RRKM model, given the expected strong resemblance between the transition states involved, whereas it agrees well with a description based on variational transition state theory. The heats of formation of the products determined with the G3 composite ab initio method show that loss of the smaller radical is without exception the more favorable reaction. The relative rates of the competing C-C bond cleavage reactions of the metastable ions vary with the number of degrees of freedom of the reactant, with the critical energy of the reaction, and with the difference between the heats of formation of the products. The presence of intermediate energy barriers when cleavage occurs at a branching point can give rise to variations in relative rates that are not easily interpreted.

Excretion of Putrescine and Spermidine by the Protein Encoded by YKL174c (TPO5) in Saccharomyces cerevisiae

The properties of the protein encoded by YKL174c (TPO5) were studied. It was found that TPO5 excretes putrescine effectively and spermidine less effectively. Gamma-aminobutyric acid slightly inhibited the excretion of putrescine, but basic amino acids did not affect excretion, suggesting that TPO5 preferentially recognizes polyamines. Accordingly, yeast cells transformed with the plasmid encoding YKL174c (TPO5) were resistant to toxicity caused by 120 mm putrescine or by 3 mm spermidine, and a mutant with a disrupted YKL174c (TPO5) gene was sensitive to toxicity by 90 mm putrescine. The growth of this mutant was faster than that of the wild-type strain. In parallel, there was an increase in putrescine and spermidine content of the YKL174c (TPO5) mutant compared with wild-type. It is noted that TPO5 functions as a suppressor of cell growth by excreting polyamines. The level of YKL174c (TPO5) mRNA was increased by the addition of polyamines to the medium. The degree of induction of the mRNA was spermine > spermidine > putrescine. The subcellular localization of TPO5 was determined by immunostaining of hemagglutinin-tagged TPO5, and it was found on Golgi or post-Golgi secretory vesicles. Excretion of putrescine and spermidine by TPO5 was reduced in cells that have mutations in the secretory or endocytic pathways, indicating that both processes are involved in the excretion of polyamines.

Molecular mechanisms of polyamine analogs in cancer cells

The natural polyamines are aliphatic cations with multiple functions and are essential for cell growth. Soon after the critical requirement of polyamines for cell proliferation was recognized, the metabolism of polyamines was pursued as a target for antineoplastic therapy. Initially, much attention was focused on the development of inhibitors of polyamine biosynthesis as a means to inhibit tumor growth. The best-characterized inhibitor is alpha-difluoromethylornithine (DFMO), an irreversible inhibitor of ornithine decarboxylase. While compensatory mechanisms in polyamine metabolism reduce the effectiveness of DFMO as a single chemotherapeutic agent, it is currently undergoing extensive testing and clinical trials for chemoprevention and other diseases. There has been increasing interest over the last two decades in the cytotoxic response to agents that target the regulation of polyamine metabolism rather than directly inhibiting the metabolic enzymes in tumor cells. This interest resulted in the development of a number of polyamine analogs that exhibit effective cytotoxicity against tumor growth in preclinical models. The analogs enter cells through a selective polyamine transport system and can be either polyamine antimetabolites that deplete the intracellular polyamines or polyamine mimetics that displace the natural polyamines from binding sites, but do not substitute in terms of growth-promoting function. Synthesis of the first generation of symmetrically substituted bis(alkyl)polyamine analogs in the mid-1980s was based on the theory that polyamines may utilize feedback mechanisms to auto-regulate their synthesis. In the 1990s, unsymmetrically substituted bis(alkyl) polyamine analogs were developed. These compounds display structure-dependent and cell type-specific cellular effects and regulation on polyamine metabolism. More recently, a novel class of analogs has been synthesized, which include conformationally restricted, cyclic and long-chain oligoamine analogs. The development and use of these analogs have provided valuable information for understanding the molecular mechanisms of targeting the polyamine pathway as a means of cancer therapy.

Low-Energy Magnetic Excitations and Morphology in Layered Hybrid Perovskite−Poly(dimethylsiloxane) Nanocomposites

Hybrid organic−inorganic layered perovskites (RnNH3)2MnCl4 of lyophilic aliphatic cations RnNH3+ (Rn = CnH2n+1; n = 2, 9) have been studied for their potential as functional additives in poly(dimet...

Endo-cavity Complexes between Calix[6]arene Dianions and Aliphatic Ammonium Cations: Structure of a Hexylammonium Complex by X-ray Crystallography

The interactions of calix[6]arene and p-tert-butylcalix[6]arene with aliphatic amines in acetonitrile solution were studied by spectrophotometric titrations in the UV region and 1H NMR spectrometry. Calix[6]arenes can undergo two deprotonations by aliphatic amines and the extent of the second proton transfer is mainly governed by the size of the α-substituent of the amine. 1H NMR spectra show that the macrocycle adopts a 1,2,3-alternate conformation and that the α-hydrogens of the ammonium ions are shielded by the π-clouds of the aromatic rings. The X-ray crystal structure of the dihexylammonium complex of the p-tert-butylcalix[6]arene dianion, reported here, confirms the 1,2,3-alternate conformation and shows one of the two ammonium moieties encapsulated in the inner cavity of the macrocycle.

C4H8[rad]+ isomerizations by theory

Structures, energies and reaction coordinates for much of the C4H8+ potential surface were obtained by ab initio and density functional theories. Most C4H8+ isomers are demonstrated to be mutually accessible below the threshold for the lowest energy dissociation, consistent with inferences from earlier experimental data. The “virtual intermediates” (point that reactions pass through corresponding to a conventional structure but lacking a corresponding potential minimum) CH3+CHCH2CH2 and +CH2CH(CH3)CH2 are found to be very important in C4H8+ rearrangements. CH3+CHCH2CH2 is accessed from the 1-butene cation by a 1,4- and a 1,2-H-shift, the 2-butene cation by a 1,2-H-shift and the 1-methylcyclopropane cation by ring opening. All reactions through CH3+CHCH2CH2 begin or end with a 1,2-H-shift going to or from the 1-butene ion. The 1-butene cation appears to form rather than the more stable 2-butene cation because the minimum energy pathways down from higher energy transition states go to the 1-butene cation side of the transition state that connects the 1-butene and the 2-butene ions. Perhaps charge localization on the CH carbon directs these pathways to the 1-butene cation by a carbocation-like rearrangement. Predicted competition between 1,3- and consecutive 1,2-transfers across double bonds, despite 1,2-shifts being energetically strongly favored over 1,3-shifts in other systems, is another interesting feature of C4H8+ reactions. The lowest energy isomerization found in this work was a 1,5-H-shift in the 1-pentene ion. In contrast to CH3+CH CH2CH2, CH3+CHCH2CH2CH2 appears to inhabit a potential energy minimum, albeit a shallow one. The order of the critical energies for different ring sized transfers is 1,4 > 1,3 ≅ 1,2 > 1,5 in the CnH2n+ ions examined, differing from the order 1,3 > 1,4 > 1,2 > 1,5 established for other homologous series of aliphatic radical cations.