The dissociative reactions; dissociation, double personality, depersonalization, amnesia, fugue states, somnambulism, and hypnosis.
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Amnesia↗
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The reaction order of the dissociation reaction of the B820 subunit of Rhodospirillum rubrum light-harvesting I complex.
We have studied the equilibrium between the dissociated B777 form (absorbing at 777 nm) of the light-harvesting complex of Rhodospirillum rubrum and the oligomeric B820 form. Analysis of the reaction order for the B820 dissociation reaction to form B777 shows that this reaction depends on the concentration of octylglucoside detergent (n-octyl-beta-D-glucopyranoside (betaOG)) present in the sample. At low betaOG concentrations (less than 1.2%) this reaction requires two components, presumably one alpha-B777 and one beta-B777, implying that the B820 subunit is a dimer. At higher betaOG concentrations this reaction requires four components, implying that B820 is a tetramer. These results partly explain the discrepancies in the literature about the stoichiometry of B820 and open an original way for studying protein-detergent interactions.
Bacterial Proteins↗
Linear relationship between activation energies and reaction energies for coverage-dependent dissociation reactions on rhodium surfaces.
Evidence of a relationship between activation energies and enthalpy changes of various dissociation reactions on transition metals has been reported recently. A reconsideration of density functional theory results for dissociation energies of oxygen and NO on different rhodium surfaces (low-index and stepped) and their dependencies on oxygen precoverage reveal that also here a linear Brønsted-Evans-Polanyi (BEP) relationship exists. The establishment of such a general concept would be of tremendous importance for the development of detailed, elementary-step reaction mechanisms, because the activation energies of reaction steps as well as their coverage dependencies could be estimated based on the adsorption energies calculated by means of DFT.
Linear Models↗
The integral encounter theory of multistage reactions containing association-dissociation reaction stages. III. Taking account of quantum states of reactants.
The formalism developed in Part I [K. L. Ivanov, N. N. Lukzen, A. A. Kipriyanov, and A. B. Doktorov, Phys. Chem. Chem. Phys. 6, 1706 (2004)] of the present contribution is extended to treat the reacting particles with internal quantum states. Initial spatial correlations of reactants are considered in the framework of this formalism as well.
Journal Article↗
Animal defensive reactions as a model for trauma-induced dissociative reactions.
Patients with complex dissociative disorders remain in alternating psychophysiological states which are discrete, discontinuous, and resistant against integrative tendencies. In this contribution, a parallel is drawn between animal defensive and recuperative states that are evoked in the face of severe threat and the characteristic responses of dissociative disorder patients as displayed in major dissociative states. Empirical data and clinical observations seem to be supportive of the idea that there are similarities between freezing, concomitant development of analgesia and anesthesia, and acute pain in threatened animals and severely traumatized human beings.
Animals↗
The role of panic in acute dissociative reactions following trauma.
OBJECTIVE: 'Peritraumatic dissociation' refers to alterations in awareness and memory for events that occur during and shortly after a traumatic experience. Despite the prevalence of reported peritraumatic dissociation, little is known about the mechanisms that mediate dissociative responses in the initial period after trauma. One theory suggests that peritraumatic dissociation may be a response to elevated arousal and panic symptoms during trauma. This study investigated panic symptoms that occurs at the time of the trauma and their relationship to ongoing dissociation in acute stress disorder. DESIGN: A sample of traumatized people with acute stress disorder or controls were administered a range of psychopathology measures within one month of their trauma. METHOD: Fifty-one civilian trauma survivors with either acute stress disorder or no acute stress disorder were administered the acute stress disorder interview, the Impact of Event Scale, the Beck Anxiety Inventory, the Peritraumatic Dissociative Experiences Questionnaire, and the Physical Reactions Scale to index panic reactions during the trauma. RESULTS: Hierarchical regression analysis found that panic reactions during the trauma accounted for nearly half of the variance (47%) of peritraumatic dissociation, and subsequent stress reactions accounted for an additional 3% of the variance. CONCLUSIONS: These findings are consistent with proposals that acute dissociation is associated with panic symptoms that occur during the traumatic experience. Possible mechanisms for the association of panic and dissociation are discussed.
Adult↗
Theory of sedimentation for ligand-mediated heterogeneous association-dissociation reactions.
Theoretical analytical sedimentation patterns have been computed for ligand-mediated heterogeneous association-dissociation reactions between macromolecules. Involvement of either a single kind of ligand or two different ligands acting in a stepwise fashion has been considered. Self-association, mediated in a stepwise fashion by two different ligands, has also been examined. The conclusion reached is that such interactions have the potentiality for exhibiting as many as three or four sedimenting peaks despite rapid rates of reaction. In general, the peaks correspond to different equilibrium compositions and not to individual macromolecular species; that is to say, they constitute a reaction boundary. Their resolution depends upon generation of concentration gradients of ligand(s) along the centrifuge cell by chemical reequilibration during sedimentation of the several macromolecular species. The implications of these findings for fundamental studies on subunit proteins and protein assemblies and for conventional applications of ultracentrifugation are discussed.
Kinetics↗
Influence of diffusion on the kinetics of excited-state association--dissociation reactions: comparison of theory and simulation.
Several recent theories of the kinetics of diffusion influenced excited-state association--dissociation reactions are tested against accurate Brownian dynamics simulation results for a wide range of parameters. The theories include the relaxation time approximation (RTA), multiparticle kernel decoupling approximations and the so-called kinetic theory. In the irreversible limit, none of these theories reduce to the Smoluchowski result. For the pseudo-first-order target problem, we show how the RTA can be modified so that the resulting formalism does reduce correctly in the irreversible limit. We call this the unified Smoluchowski approximation, because it unites modern theories of reversible reactions with Smoluchowski's theory of irreversible reactions.
Computer Simulation↗
Nucleophilic substitution reactions at liquid/liquid interfaces: molecular dynamics simulation of a model S(N)1 dissociation reaction at the water/carbon tetrachloride interface.
The ionic dissociation step of the nucleophilic substitution reaction t-BuCl --> t-Bu(+) + Cl(-) is studied at the water/carbon tetrachloride interface using molecular dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. The umbrella sampling technique is used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) at several interface regions of varying distances from the Gibbs dividing surface. We find a significant increase of the ionic dissociation barrier height and of the reaction free energy at the interface relative to bulk water. This is shown to be due to the reduced polarity of the interface which causes a destabilization of the pure ionic state. However, deformation to the neat interface structure in the form of water protrusions into the organic phase may provide partial stabilization of the ionic species. The importance of these structural effects is examined by repeating the calculations with an artificially smooth interface. The destabilization of the ionic state at the interface also manifests itself with a rapid (picosecond time scale) recombination dynamics of the ions to form the parent molecule followed by a slow vibrational relaxation.
Journal Article↗
Protein import into nuclei: association and dissociation reactions involving transport substrate, transport factors, and nucleoporins.
The molecular dynamics of nuclear protein import were examined in a solution binding assay by testing for interactions between a protein containing a nuclear localization signal (NLS), the transport factors karyopherin alpha, karyopherin beta, and Ran, and FXFG or GLFG repeat regions of nucleoporins. We found that karyopherins alpha and beta cooperate to bind FXFG but not GLFG repeat regions. Binding of the NLS protein to karyopherin alpha was enhanced by karyopherin beta. Two novel reactions were discovered. First, incubation of a karyopherin heterodimer-NLS protein complex with an FXFG repeat region stimulated the dissociation of the NLS protein from the karyopherin heterodimer. Second, incubation of the karyopherin heterodimer with RanGTP (or with a Ran mutant that cannot hydrolyze GTP) led to the dissociation of karyopherin alpha from beta and to an association of Ran with karyopherin beta; RanGDP had no effect. We propose that movement of NLS proteins across the nuclear pore complex is a stochastic process that operates via repeated association-dissociation reactions.
Amino Acid Sequence↗
Applications of electron-ion dissociation reactions for analysis of polycationic chitooligosaccharides in Fourier transform mass spectrometry.
Singly protonated, doubly protonated, and sodiated pentaglucosamide (GlcNAc)(5), oligoglucosamines (GlcN)(m)(), and (GlcN)(3)GlcN(3OH14:0) were analyzed in an FTICR mass spectrometer by electron-ion dissociation reactions and compared to collision activation. The general fragmentation mode was found as the asymmetrical sequence fragments (B(n)() and minor C(n)() ion series) with full sequence coverage. Molecular mass information of each glucosamide or glucosamine residue can be readily obtained from the ion series. Fragmentation by electron capture dissociation revealed additional fragmentation of the N-acetyl moiety compared to sustained off-resonance irradiation collision-activated dissociation (SORI-CAD) and electron-induced dissociation (EID). Sodiated GlcNAc(5) molecular adduct ions were analyzed by EID and compared to CAD. Both techniques provided full sequence coverage. EID was more effective, but CAD resulted in the cross-ring ion products (0,2)A(n)() and (2,4)A(n)() for all relevant glucosamide residues.
Journal Article↗
Yeast hexokinase: substrate-induced association--dissociation reactions in the binding of glucose to hexokinase P-II.
A method is described for the purification of native hexokinases P-I and P-II from yeast using preparative isoelectric focussing to separate the isozymes. The binding of glucose to hexokinase P-II, and the effect of this on the monomer--dimer association--dissociation reaction have been investigated quantitatively by a combination of titrations of intrinsic protein fluorescence and equilibrium ultracentrifugation. Association constants for the monomer-dimer reaction decreased with increasing pH, ionic strength and concentration of glucose. Saturating concentrations of glucose did not bring about complete dissociation of the enzyme showing that both sites were occupired in the dimer. At pH 8.0 and high ionic strength, where the enzyme existed as monomer, the dissociation constant of the enzyme-glucose complex was 3 X 10(-4) mol 1(-1) and was independent of the concentration of enzyme. Binding to the dimeric form at low pH and ionic strength (I=0.02 mol 1(-1), pH less than 7.5) was also independent of enzyme concentration (in the range 10-1000 mug ml-1) but was much weaker. The process could be described by a single dissociation constant, showing that the two available sites on the dimer were equivalent and non-cooperative; values of the intrinsic dissociation constant varied from 2.5 X 10(-3) mol 1(-1) at pH 7.0 to 6 X 10(-3) at pH 6.5. Under intermediate conditions (pH 7.0, ionic strength=0.15 mol 1(-1)), where monomer and dimer coexisted, the binding of glucose showed weak positive cooperatively (Hill coefficient 1.2); in addition, the binding was dependent upon the concentration of enzyme in the direction of stronger binding at lower concentrations. The results show that the phenomenon of half-sites reactivity observed in the binding of glucose to crystalline hexokinase P-II does not occur in solution; the simplest explanation of our finding the two sites to be equivalent is that the dimer results from the homologous association of two identical subunits.
Binding Sites↗
Dissociation reactions of gaseous ferro-, ferri-, and apo-cytochrome c ions.
Electrochemical reduction of the iron bound in the heme group of cytochrome c is shown to occur in the nano-electrospray capillary if the protein is sprayed from neutral water using a steel wire as the electrical contact. Quadrupole ion trap collisional activation is used to study the dissociation reactions of cytochrome c as a function of the oxidation state of the iron. Oxidized (Fe(III)) cytochrome c dissociates via sequence-specific amide bond cleavage, while the reduced (Fe(II)) form of the protein dissociates almost exclusively by loss of protonated heme. Apo-cytochrome c, from which the heme has been removed either via gas-phase dissociation of the reduced holo-protein or via solution chemistry, dissociates via amide bond cleavage in similar fashion to the oxidized holo-protein.
Apoproteins↗
Ion dissociation reactions induced in a high-pressure quadrupole collision cell.
This work concerns a new high-pressure quadrupole collision cell, designed for triple-quadrupole mass spectrometers. This new collision cell operates at pressures up to 10 mTorr, an order of magnitude higher than conventional cells of this type. Previous investigations have concentrated upon the significant increases in transmission efficiency and in resolving power for fragment ions which result from the use of this new design. The present work reports an investigation into the nature of the dissociation reactions which can be induced by collisions in this high-pressure cell. Charge-site-remote fragmentations of a simple precursor ion were chosen as a test case, and were found to be observable at laboratory collision energies lower by a factor of 4-5 than those found previously to be necessary when using conventional low-pressure quadrupole collision cells. It was also shown that the charge-site-remote reactions were accompanied by the mixed-site-fragmentation reactions described by Tuinman and Cook (J. Am. Soc. Mass Spectrom. Vol. 1, p. 85 (1989)). Ionization of collision gas was observed in the case of xenon. Efforts to observe charge-site-remote fragmentations of peptide ions were marginally successful. Highly basic peptides, which have been problematic for sequencing by low-energy tandem mass spectrometry, did not yield useful fragment-ion spectra in the new cell. The fragmentation behaviour of protonated Leu-enkephalin, for which fragmentation pathways have been thoroughly studied previously, suggested that the observed spectra reflected integration of the fragmentation kinetics over a considerably longer time, thus involving many more reaction steps. These combined observations are considered in terms of a qualitative model based on a rapid decrease of ion kinetic energy during passage through the cell, with much longer residence times than for conventional quadrupole cells.
Amino Acid Sequence↗
Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.
The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.
Journal Article↗
Rotational effects in broadening factors of fall-off curves of unimolecular dissociation reactions.
Strong collision fall-off curves of unimolecular dissociation and the reverse recombination reactions are calculated by using the statistical adiabatic channel/classical trajectory model (SACM/CT). This formalism properly accounts for angular momentum coupling of transitional modes with overall rotation. Calculations are made for linear molecules dissociating into linear fragments and atoms with randomly chosen properties of the transitional modes and for isotropic as well as anisotropic potentials. Analytical representations of center broadening factors as a function of molecular parameters are given. A comparison between fall-off curves from rigid activated complex RRKM theory, from the present loose activated complex SACM/CT model, and from CT calculations on an ab initio potential is made for the HO2-->H + O2 system. It is shown that, besides rotational effects, energy-dependent anharmonicities of the density of states also influence the shape of the fall-off curves in this system.
Journal Article↗
Pressure-jump relaxation studies of the association--dissociation reaction of E. coli ribosomes.
The association--dissociation kinetics of ribosomal particles from E. coli have been studied using a pressure-jump apparatus with optical detection. Experiments on isolated subunits yield two relaxation times of about 10 and 700 ms, respectively. With mixtures of 30 S and 50 S particles an additional relaxation time of about 100 ms is observed, which is assigned to the equilibrium 30 S + 50 S in equilibrium 70 S. The two other times are attributed to reversible equilibria between subunit monomers and subunit homo-associates.
Binding Sites↗
[Changes in indices of the morphologic dissociation reaction of clotted blood in the most acute period of ischemic stroke].
Examinations of the changes in the parameters of the reaction of clotted blood morphological dissociation (CBMDR) occuring in the acutest period of ischemic cerebral stroke were carried out over time. Regular changes of those parameters were revealed, these changes depending on the disease gravity and time course. In graver forms and course of the ischemic stroke a diminution of the volume of the IIId blood-clotting fraction and a shortening of the time of its formation were observed. As the patients' state improved in the course of the conservative treatment given, the above parameters gradually approached those observed in the control group. On the contrary a deterioration of the patients' state led to a rapid diminution of the IIId fraction volume and shortening of the time of its formation. The changes of the CBMDR parameters allow one to judge about the gravity of ischemic cerebral stroke and the time course of the pathological process, as well as to assess the efficacy of the therapy given.
Acute Disease↗