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Sample records for combined pulsed-q dissociation

  1. Combined Pulsed-Q dissociation and electron transfer dissociation for identification and quantitation of iTRAQ–labeled phosphopeptides

    SciTech Connect

    Yang, Feng; Wu, Si; Stenoien, David L.; Zhao, Rui; Monroe, Matthew E.; Gritsenko, Marina A.; Purvine, Samuel O.; Polpitiya, Ashoka D.; Tolic, Nikola; Zhang, Qibin; Norbeck, Angela D.; Orton, Daniel J.; Moore, Ronald J.; Tang, Keqi; Anderson, Gordon A.; Pasa-Tolic, Ljiljana; Camp, David G.; Smith, Richard D.

    2009-05-15

    Multiplex isobaric tags for relative and absolute quantification (iTRAQ) enable high-throughput quantification of peptides via reporter ion signals in the low mass range of tandem mass spectra. A challenging but highly promising application is to analyze iTRAQ-labeled peptides using a sensitive linear ion trap mass spectrometer (LTQ-MS) and pulsed Q dissociation (PQD), a form of ion trap collision activated dissociation (CAD) designed to allow detection of low mass-to-charge fragment ions. Electron dissociation transfer (ETD), on the other hand, is complementary to PQD and is especially useful for sequencing peptides containing post-translational modifications (PTMs). Here, we developed an integrated workflow for robust and accurate quantitative identification of iTRAQ labeled phosphopeptides that integrates the PQD and ETD fragmentation methods together with PQD optimization, data management and bioinformatics tools. Analysis of the phosphoproteome of human fibroblast cells demonstrated that this hybrid mode is superior to either PQD or ETD alone for phosphopeptide identification and quantitation. The combined PQD/ETD approach can qualitatively identify additional phosphopeptides than ETD alone and PQD information can provide better quantitation of ETD identified iTRAQ-labeled phosphopeptides.

  2. Combined Pulsed-Q dissociation and electron transfer dissociation for identification and quantification of iTRAQ–labeled phosphopeptides

    PubMed Central

    Yang, Feng; Wu, Si; Stenoien, David L.; Zhao, Rui; Monroe, Matthew E.; Gristenko, Marina A.; Purvine, Samuel O.; Polpitiya, Ashoka D.; Tolić, Nikola; Zhang, Qibin; Norbeck, Angela D.; Orton, Daniel J.; Moore, Ronald J.; Tang, Keqi; Anderson, Gordon A.; Paša-Tolić, Ljiljana; Camp, David G.; Smith, Richard D.

    2009-01-01

    Here, we report a new approach that integrates pulsed Q dissociation (PQD) and electron transfer dissociation (ETD) techniques for confident and quantitative identification of iTRAQ-labeled phosphopeptides. The use of isobaric tags for relative and absolute quantification enables a high-throughput quantification of peptides via reporter ion signals in the low m/z range of tandem mass spectra. PQD, a form of ion trap collision activated dissociation allows for detection of low mass-to-charge fragment ions and electron transfer dissociation is especially useful for sequencing peptides that contain post-translational modifications. Analysis of the phosphoproteome of human fibroblast cells using a sensitive linear ion trap mass spectrometer demonstrated that this hybrid approach improves both identification and quantification of phosphopeptides. ETD improved phosphopeptide identification, while PQD provides improved quantification of iTRAQ-labeled phosphopeptides. PMID:19371082

  3. Combined Infrared Multiphoton Dissociation with Ultraviolet Photodissociation for Ubiquitin Characterization

    NASA Astrophysics Data System (ADS)

    Halim, Mohammad A.; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2016-09-01

    Herein we report the successful implementation of the consecutive and simultaneous photodissociation with high (213 nm) and low (10.6 μm) energy photons (HiLoPD, high-low photodissociation) on ubiquitin in a quadrupole-Orbitrap mass spectrometer. Absorption of high-energy UV photon is dispersed over the whole protein and stimulates extensive C-Cα backbone fragmentation, whereas low-energy IR photon gradually increases the internal energy and thus preferentially dissociates the most labile amide (C-N) bonds. We noticed that simultaneous irradiation of UV and IR lasers on intact ubiquitin in a single MS/MS experiment provides a rich and well-balanced fragmentation array of a/x, b/y, and z ions. Moreover, secondary fragmentation from a/x and z ions leads to the formation of satellite side-chain ions (d, v, and w) and can help to distinguish isomeric residues in a protein. Implementation of high-low photodissociation in a high-resolution mass spectrometer may offer considerable benefits to promote a comprehensive portrait of protein characterization.

  4. Dissociation constant measurement using combination tapered fiber optic biosensor (CTFOB) dip-probes

    NASA Astrophysics Data System (ADS)

    Wang, Chun-Wei; Kapoor, Rakesh

    2010-02-01

    The document reports a novel method of measuring dissociation constant (kD) of antibody-antigen interaction using evanescent wave based combination tapered fiber-optic biosensor (CTFOB) dip-probes. The method was demonstrated by measuring the dissociation constant of human Interleukin-6 (IL-6) and anti-IL-6 interaction. Sandwich immunoassay was used to generate fluorescence signal proportional to antigen-antibody conjugate pairs. A portable CCD based spectrometer setup was used to record spectral profile of the fluorescence signal. The measured value of dissociation constant kD for IL-6 and capture anti-IL-6 (clone MQ2-13A5) antibodies at room temperature is588 +/-19 pM .

  5. Combining fixed- and moving-grid methods to study direct dissociation processes involving nonadiabatic transitions

    SciTech Connect

    Gindensperger, Etienne; Meier, Christoph; Beswick, J. Alberto; Parlant, Gerard

    2005-12-01

    We present a novel quantum-dynamics approach suitable for computing direct dissociation processes, including electronic transitions. This approach combines quantum trajectories in the Lagrangian reference frame with standard fixed-grid wave packets in order to overcome the limitations and difficulties of both techniques. As a model application, we consider the ultrafast photodissociation of H{sub 2} excited by a femtosecond extreme UV laser pulse.

  6. A combination thermal dissociation/electron impact ionization source for RIB generation

    SciTech Connect

    Alton, G.D.; Cui, B.; Welton, R.F.

    1996-12-31

    The flourishing interest in radioactive ion beams (RIBs) with intensities adequate for astrophysics and nuclear physics research place a premium on targets that will swiftly release trace amounts of short lived radio-nuclei in the presence of bulk quantities of target material and ion sources that have the capability of efficiently ionizing the release products. Because of the low probability of simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecules containing the element of interest with conventional, hot-cathode, electron-impact ion sources, the species of interest is often distributed in several mass channels in the form of molecular sideband beams and, consequently, the intensity is diluted. The authors have conceived an ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high efficiency characteristics of an electron impact ionization source to address these problems. If the concept proves to be a viable option, the source will be used as a complement to the electron beam plasma ion sources already in use at the HRIBF. The design features and principles of operation of the source are described in this article.

  7. Dissociative disorder induced by clarithromycin combined with rabeprazole in a patient with gastritis.

    PubMed

    Feng, Zhixian; Huang, Jinwen; Xu, Yi; Zhang, Minming; Hu, Shaohua

    2013-02-01

    Clarithromycin and rabeprazole are both valued for their safety profile. Very few cases of adverse side-effects related to these drugs, when given individually, have been reported; serious side-effects of clarithromycin in combination with rabeprazole have never been reported. The present case reports on a 51-year-old woman with gastritis who received clarithromycin combined with rabeprazole for Helicobacter pylori infection. After taking 500 mg clarithromycin and 10 mg rabeprazole orally she displayed acute psychotic symptoms of dissociative disorder, including: impairment of orientation and attention; the feeling of dreaming; disintegration of thinking; stereotyped speech; flattened emotion; amnesia. Routine blood investigations, computed tomography scans and electroencephalography showed no abnormalities. All symptoms disappeared without antipsychotic treatment ≈ 48 h after she had taken the two drugs. Combining clarithromycin with rabeprazole might increase the risk of neurotoxicity, particularly in susceptible individuals. This should be a concern in clinical practice.

  8. Combined impact of entropy and carrier delocalization on charge transfer exciton dissociation at the donor-acceptor interface

    NASA Astrophysics Data System (ADS)

    Ono, Shota; Ohno, Kaoru

    2016-08-01

    Several models of the charge transfer exciton (CTE) have been proposed to explain its dissociation at the donor-acceptor (DA) interface. However, the underlying physics is still under debate. Here, we derive a temperature (T ) dependent tight-binding model for an electron-hole pair at the DA interface. The main finding is the existence of the localization-delocalization transition at a critical T , which can explain the CTE dissociation. The present study highlights the combined effect of entropy (finite T ) and carrier delocalization in the CTE dissociation.

  9. Combined infrared multiphoton dissociation and electron capture dissociation with a hollow electron beam in Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Tsybin, Youri O; Witt, Matthias; Baykut, Gökhan; Kjeldsen, Frank; Håkansson, Per

    2003-01-01

    An electron injection system based on an indirectly heated ring-shaped dispenser cathode has been developed and installed in a 7 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. This new hardware design allows high-rate electron capture dissociation (ECD) to be carried out by a hollow electron beam coaxial with the ion cyclotron resonance (ICR) trap. Infrared multiphoton dissociation (IRMPD) can also be performed with an on-axis IR-laser beam passing through a hole at the centre of the dispenser cathode. Electron and photon irradiation times of the order of 100 ms are required for efficient ECD and IRMPD, respectively. As ECD and IRMPD generate fragments of different types (mostly c, z and b, y, respectively), complementary structural information that improves the characterization of peptides and proteins by FTICR mass spectrometry can be obtained. The developed technique enables the consecutive or simultaneous use of the ECD and IRMPD methods within a single FTICR experimental sequence and on the same ensemble of trapped ions in multistage tandem (MS/MS/MS or MS(n)) mass spectrometry. Flexible changing between ECD and IRMPD should present advantages for the analysis of protein digests separated by liquid chromatography prior to FTICRMS. Furthermore, ion activation by either electron or laser irradiation prior to, as well as after, dissociation by IRMPD or ECD increases the efficiency of ion fragmentation, including the w-type fragment ion formation, and improves sequencing of peptides with multiple disulfide bridges. The developed instrumental configuration is essential for combined ECD and IRMPD on FTICR mass spectrometers with limited access into the ICR trap. PMID:12872281

  10. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    NASA Astrophysics Data System (ADS)

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-01

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O-/OH- and CH3- are recorded, indicating the low kinetic energies of O-/OH- for ethanol while the low and high kinetic energy distributions of O- ions for acetaldehyde. The CH3- image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O- ion via the dehydrogenated intermediate, CH3CHO- (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH3- is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  11. Modeling pure methane hydrate dissociation using a numerical simulator from a novel combination of X-ray computed tomography and macroscopic data

    SciTech Connect

    Gupta, A.; Moridis, G.J.; Kneafsey, T.J.; Sloan, Jr., E.D.

    2009-08-15

    The numerical simulator TOUGH+HYDRATE (T+H) was used to predict the transient pure methane hydrate (no sediment) dissociation data. X-ray computed tomography (CT) was used to visualize the methane hydrate formation and dissociation processes. A methane hydrate sample was formed from granular ice in a cylindrical vessel, and slow depressurization combined with thermal stimulation was applied to dissociate the hydrate sample. CT images showed that the water produced from the hydrate dissociation accumulated at the bottom of the vessel and increased the hydrate dissociation rate there. CT images were obtained during hydrate dissociation to confirm the radial dissociation of the hydrate sample. This radial dissociation process has implications for dissociation of hydrates in pipelines, suggesting lower dissociation times than for longitudinal dissociation. These observations were also confirmed by the numerical simulator predictions, which were in good agreement with the measured thermal data during hydrate dissociation. System pressure and sample temperature measured at the sample center followed the CH{sub 4} hydrate L{sub w}+H+V equilibrium line during hydrate dissociation. The predicted cumulative methane gas production was within 5% of the measured data. Thus, this study validated our simulation approach and assumptions, which include stationary pure methane hydrate-skeleton, equilibrium hydrate-dissociation and heat- and mass-transfer in predicting hydrate dissociation in the absence of sediments. It should be noted that the application of T+H for the pure methane hydrate system (no sediment) is outside the general applicability limits of T+H.

  12. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    SciTech Connect

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-14

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O{sup −}/OH{sup −} and CH{sub 3}{sup −} are recorded, indicating the low kinetic energies of O{sup −}/OH{sup −} for ethanol while the low and high kinetic energy distributions of O{sup −} ions for acetaldehyde. The CH{sub 3}{sup −} image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O{sup −} ion via the dehydrogenated intermediate, CH{sub 3}CHO{sup −} (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH{sub 3}{sup −} is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  13. A combined electron-ion spectrometer for studying complete kinematics of molecular dissociation upon shell selective ionization

    SciTech Connect

    Saha, K.; Banerjee, S. B.; Bapat, B.

    2013-07-15

    A combined electron-ion spectrometer has been built to study dissociation kinematics of molecular ions upon various electronic decay processes ensuing from ionization of neutral molecules. The apparatus can be used with various ionization agents. Ion time-of-flight (ToF) spectra arising from various electronic decay processes are acquired by triggering the ToF measurement in coincidence with energy analyzed electrons. The design and the performance of the spectrometer in a photoionization experiment is presented in detail. Electron spectra and ion time of flight spectra resulting from valence and 2p{sub 1/2} ionization of Argon and those from valence ionization of CO are presented to demonstrate the capability of the instrument. The fragment ion spectra show remarkable differences (both kinematic and cross sectional) dependent on the energy of the ejected electron, corresponding to various electron loss and decay mechanisms in dissociative photoionization of molecules.

  14. Effect of Basic Residue on the Kinetics of Peptide Fragmentation Examined Using Surface-Induced Dissociation Combined with Resonant Ejection

    SciTech Connect

    Laskin, Julia

    2015-11-30

    In this work, resonant ejection coupled with surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer is used to examine fragmentation kinetics of two singly protonated hexapeptides, RYGGFL and KYGGFL, containing the basic arginine residue and less basic lysine residue at the N-terminus. The kinetics of individual reaction channels at different collision energies are probed by applying a short ejection pulse (1 ms) in resonance with the cyclotron frequency of a selected fragment ion and varying the delay time between ion-surface collision and resonant ejection while keeping total reaction delay time constant. Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data provides accurate threshold energies and activation entropies of individual reaction channels. Substitution of arginine with less basic lysine has a pronounced effect on the observed fragmentation kinetics of several pathways, including the b2 ion formation, but has little or no effect on formation of the b5+H2O fragment ion. The combination of resonant ejection SID, time- and collision energy-resolved SID, and RRKM modeling of both types of experimental data provides a detailed mechanistic understanding of the primary dissociation pathways of complex gaseous ions.

  15. Dissociable neural representations of grammatical gender in Broca's area investigated by the combination of satiation and TMS.

    PubMed

    Cattaneo, Zaira; Devlin, Joseph T; Vecchi, Tomaso; Silvanto, Juha

    2009-08-15

    Along with meaning and form, words can be described on the basis of their grammatical properties. Grammatical gender is often used to investigate the latter as it is a grammatical property that is independent of meaning. The left inferior frontal gyrus (IFG) has been implicated in the encoding of grammatical gender, but its causal role in this process in neurologically normal observers has not been demonstrated. Here we combined verbal satiation with transcranial magnetic stimulation (TMS) to demonstrate that subpopulations of neurons within Broca's area respond preferentially to different classes of grammatical gender. Subjects were asked to classify Italian nouns into living and nonliving categories; half of these words were of masculine and the other half of feminine grammatical gender. Prior to each test block, a satiation paradigm (a phenomenon in which verbal repetition of a category name leads to a reduced access to that category) was used to modulate the initial state of the representations of either masculine or feminine noun categories. In the No TMS condition, subjects were slower in responding to exemplars to the satiated category relative to exemplars of the nonsatiated category, implying that the neural representations for different classes of grammatical gender are partly dissociable. The application of TMS over Broca's area removed the behavioral impact of verbal (grammatical) satiation, demonstrating the causal role of this region in the encoding of grammatical gender. These results show that the neural representations for different cases of a grammatical property within Broca's area are dissociable. PMID:19442750

  16. Combined Use of Post-Ion Mobility/Collision-Induced Dissociation and Chemometrics for b Fragment Ion Analysis

    NASA Astrophysics Data System (ADS)

    Zekavat, Behrooz; Miladi, Mahsan; Becker, Christopher; Munisamy, Sharon M.; Solouki, Touradj

    2013-09-01

    Although structural isomers may yield indistinguishable ion mobility (IM) arrival times and similar fragment ions in tandem mass spectrometry (MS), it is demonstrated that post-IM/collision-induced dissociation MS (post-IM/CID MS) combined with chemometrics can enable independent study of the IM-overlapped isomers. The new approach allowed us to investigate the propensity of selected b type fragment ions from AlaAlaAlaHisAlaAlaAla-NH2 (AAA(His)AAA) heptapeptide to form different isomers. Principle component analysis (PCA) of the unresolved post-IM/CID profiles indicated the presence of two different isomer types for b4 +, b5 +, and b6 + and a single isomer type for b7 + fragments of AAA(His)AAA. We employed a simple-to-use interactive self-modeling mixture analysis (SIMPLISMA) to calculate the total IM profiles and CID mass spectra of b fragment isomers. The deconvoluted CID mass spectra showed discernible fragmentation patterns for the two isomers of b4 +, b5 +, and b6 + fragments. Under our experimental conditions, calculated percentages of the "cyclic" isomers (at the 95 % confidence level for n = 3) for b4 +, b5 +, and b6 + were 61 (± 5) %, 36 (± 5) %, and 48 (± 2) %, respectively. Results from the SIMPLISMA deconvolution of b5 + species resembled the CID MS patterns of fully resolved IM profiles for the two b5 + isomers. The "cyclic" isomers for each of the two-component b fragment ions were less susceptible to ion fragmentation than their "linear" counterparts.

  17. Dissociative disorders.

    PubMed

    Kihlstrom, John F

    2005-01-01

    The dissociative disorders, including "psychogenic" or "functional" amnesia, fugue, dissociative identity disorder (DID, also known as multiple personality disorder), and depersonalization disorder, were once classified, along with conversion disorder, as forms of hysteria. The 1970s witnessed an "epidemic" of dissociative disorder, particularly DID, which may have reflected enthusiasm for the diagnosis more than its actual prevalence. Traditionally, the dissociative disorders have been attributed to trauma and other psychological stress, but the existing evidence favoring this hypothesis is plagued by poor methodology. Prospective studies of traumatized individuals reveal no convincing cases of amnesia not attributable to brain insult, injury, or disease. Treatment generally involves recovering and working through ostensibly repressed or dissociated memories of trauma; at present, there are few quantitative or controlled outcome studies. Experimental studies are few in number and have focused largely on state-dependent and implicit memory. Depersonalization disorder may be in line for the next "epidemic" of dissociation.

  18. Dissociative amnesia.

    PubMed

    Staniloiu, Angelica; Markowitsch, Hans J

    2014-08-01

    Dissociative amnesia is one of the most enigmatic and controversial psychiatric disorders. In the past two decades, interest in the understanding of its pathophysiology has surged. In this report, we review new data about the epidemiology, neurobiology, and neuroimaging of dissociative amnesia and show how advances in memory research and neurobiology of dissociation inform proposed pathogenetic models of the disorder. Dissociative amnesia is characterised by functional impairment. Additionally, preliminary data suggest that affected people have an increased and possibly underestimated suicide risk. The prevalence of dissociative amnesia differs substantially across countries and populations. Symptoms and disease course also vary, indicating a possibly heterogeneous disorder. The accompanying clinical features differ across cultural groups. Most dissociative amnesias are retrograde, with memory impairments mainly involving the episodic-autobiographical memory domain. Anterograde dissociative amnesia occurring without significant retrograde memory impairments is rare. Functional neuroimaging studies of dissociative amnesia with prevailing retrograde memory impairments show changes in the network that subserves autobiographical memory. At present, no evidence-based treatments are available for dissociative amnesia and no broad framework exists for its rehabilitation. Further research is needed into its neurobiology, course, treatment options, and strategies to improve differential diagnoses.

  19. Separation and identification of phosphatidylcholine regioisomers by combining liquid chromatography with a fusion of collision-and ozone-induced dissociation.

    PubMed

    Mitchell, Todd; Blanksby, Stephen; Kozlowskia, Rachel

    2015-01-01

    The differentiation of closely related lipid isomers is increasingly important to our evolving understanding of lipid biochemistry but it is equally challenging to contemporary chromatographic and mass spectral analyses. Recently, we described a novel ion-activation approach based on combining collision- with ozone-induced dissociation (CID/OzID) for the identification of the relative acyl chain substitution positions in glycerophospholipids. Here we demonstrate, for the first time, that CID/OzID can be effectively combined with reversed-phase chromatography to enable the separation and unambiguous identification of regioisomeric pairs of phosphatidylcholines that differ only in the arrangement of acyl chains on the glycerol backbone. PMID:26307699

  20. New Approach for Studying Slow Fragmentation Kinetics in FT-ICR: Surface-Induced Dissociation Combined with Resonant Ejection

    SciTech Connect

    Laskin, Julia; Futrell, Jean H.

    2015-02-01

    We introduce a new approach for studying the kinetics of large ion fragmentation in the gas phase by coupling surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer with resonant ejection of selected fragment ions using a relatively short (5 ms) ejection pulse. The approach is demonstrated for singly protonated angiotensin III ions excited by collisions with a self-assembled monolayer of alkylthiol on gold (HSAM). The overall decomposition rate and rate constants of individual reaction channels are controlled by varying the kinetic energy of the precursor ion in a range of 65–95 eV. The kinetics of peptide fragmentation are probed by varying the delay time between resonant ejection and fragment ion detection at a constant total reaction time. RRKM modeling indicates that the shape of the kinetics plots is strongly affected by the shape and position of the energy deposition function (EDF) describing the internal energy distribution of the ion following ion-surface collision. Modeling of the kinetics data provides detailed information on the shape of the EDF and energy and entropy effects of individual reaction channels.

  1. Dissociation of C{sub 3}H{sub 3}I and rates for C{sub 3}H{sub 3} combination at high temperatures.

    SciTech Connect

    Tranter, R. S.; Yang, X.; Kiefer, J. H.

    2010-01-01

    The decomposition of propargyl iodide, C{sub 3}H{sub 3}I {yields} C{sub 3}H{sub 3} + I, and the following combination of propargyl radical, C{sub 3}H{sub 3} + C{sub 3}H{sub 3} {yields} C{sub 6}H{sub 6}, have been observed in the incident shock in mixtures of 1%, 2%, and 5% C{sub 3}H{sub 3}I in Kr, over 800-2000 K, for nominal post-shock pressures of 20 and 130 Torr. The iodide dissociates readily, the endothermic reaction producing an easily resolved positive density gradient whose kinetic modeling allows extraction of precise rates showing strong falloff. A simple Gorin-model RRKM treatment of the measurements results in a k{sub {infinity}} = 3.35 x 10{sup 18} T{sup -0.9}exp{sup (-22192/T)} s{sup -1}. The initial positive gradient is immediately followed by a strong negative, showing exothermic reaction from propargyl combination. Modeling of this gradient with an assumed theoretical product distribution, provided by J.A. Miller, results in propargyl combination rates in excellent agreement with current theory and having a strong negative temperature dependence, the rate dropping near a factor of forty over 800-2000 K. Possible errors associated with the need to assume a product distribution are discussed and it is suggested that this should not result in rate uncertainties for the C{sub 3}H{sub 3} combination reaction greater than {+-}50%.

  2. An application of the novel quantum mechanical/molecular mechanical method combined with the theory of energy representation: An ionic dissociation of a water molecule in the supercritical water.

    PubMed

    Takahashi, Hideaki; Satou, Wataru; Hori, Takumi; Nitta, Tomoshige

    2005-01-22

    A novel quantum chemical approach recently developed has been applied to an ionic dissociation of a water molecule (2H(2)O-->H(3)O(+)+OH(-)) in ambient and supercritical water. The method is based on the quantum mechanical/molecular mechanical (QM/MM) simulations combined with the theory of energy representation (QM/MM-ER), where the energy distribution function of MM solvent molecules around a QM solute serves as a fundamental variable to determine the hydration free energy of the solute according to the rigorous framework of the theory of energy representation. The density dependence of the dissociation free energy in the supercritical water has been investigated for the density range from 0.1 to 0.6 g/cm(3) with the temperature fixed at a constant. It has been found that the product ionic species significantly stabilizes in the high density region as compared with the low density. Consequently, the dissociation free energy decreases monotonically as the density increases. The decomposition of the hydration free energy has revealed that the entropic term (-TDeltaS) strongly depends on the density of the solution and dominates the behavior of the dissociation free energy with respect to the variation of the density. The increase in the entropic term in the low density region can be attributed to the decrease in the translational degrees of freedom brought about by the aggregation of solvent water molecules around the ionic solute.

  3. Dissociative disorders in DSM-5.

    PubMed

    Spiegel, David; Lewis-Fernández, Roberto; Lanius, Ruth; Vermetten, Eric; Simeon, Daphne; Friedman, Matthew

    2013-01-01

    The rationale, research literature, and proposed changes to the dissociative disorders and conversion disorder in the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) are presented. Dissociative identity disorder will include reference to possession as well as identity fragmentation, to make the disorder more applicable to culturally diverse situations. Dissociative amnesia will include dissociative fugue as a subtype, since fugue is a rare disorder that always involves amnesia but does not always include confused wandering or loss of personality identity. Depersonalization disorder will include derealization as well, since the two often co-occur. A dissociative subtype of posttraumatic stress disorder (PTSD), defined by the presence of depersonalization or derealization in addition to other PTSD symptoms, is being recommended, based upon new epidemiological and neuroimaging evidence linking it to an early life history of adversity and a combination of frontal activation and limbic inhibition. Conversion disorder (functional neurological symptom disorder) will likely remain with the somatic symptom disorders, despite considerable dissociative comorbidity. PMID:23394228

  4. Dissociative disorders in DSM-5.

    PubMed

    Spiegel, David; Lewis-Fernández, Roberto; Lanius, Ruth; Vermetten, Eric; Simeon, Daphne; Friedman, Matthew

    2013-01-01

    The rationale, research literature, and proposed changes to the dissociative disorders and conversion disorder in the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) are presented. Dissociative identity disorder will include reference to possession as well as identity fragmentation, to make the disorder more applicable to culturally diverse situations. Dissociative amnesia will include dissociative fugue as a subtype, since fugue is a rare disorder that always involves amnesia but does not always include confused wandering or loss of personality identity. Depersonalization disorder will include derealization as well, since the two often co-occur. A dissociative subtype of posttraumatic stress disorder (PTSD), defined by the presence of depersonalization or derealization in addition to other PTSD symptoms, is being recommended, based upon new epidemiological and neuroimaging evidence linking it to an early life history of adversity and a combination of frontal activation and limbic inhibition. Conversion disorder (functional neurological symptom disorder) will likely remain with the somatic symptom disorders, despite considerable dissociative comorbidity.

  5. Dissociative phenomenology of dissociative identity disorder.

    PubMed

    Dell, Paul F

    2002-01-01

    The goal of this study was to investigate the dissociative phenomenology of dissociative identity disorder (DID). The Multidimensional Inventory of Dissociation (MID) was administered to 34 patients with DID, 23 patients with dissociative disorder not otherwise specified (DDNOS), 52 patients with mixed psychiatric disorders, and 58 normal individuals. DID patients obtained significantly higher scores than the other three groups on 27 dissociation-related variables. DDNOS patients had significantly higher scores than normals and mixed psychiatric patients on 17 and 15 dissociation-related variables, respectively. The findings of the present study are virtually identical to a large body of replicated findings about the dissociative phenomenology of DID. This broad range of dissociation-related phenomena, which routinely occurs in individuals with DID, is largely absent from the DSM-IV-TR account of DID. Factor analysis of the 11 dimensions of dissociation that are measured by the MID extracted only one factor that accounted for 85% of the variance. It was concluded that dissociation is a unifactorial taxon or natural type that has different aspects or epiphenomena (i.e., amnesia, depersonalization, voices, trance, etc.).

  6. A Combined Theoretical and Experimental Study of Dissociation of Charge Transfer States at the Donor-Acceptor Interface of Organic Solar Cells.

    PubMed

    Tscheuschner, Steffen; Bässler, Heinz; Huber, Katja; Köhler, Anna

    2015-08-13

    The observation that in efficient organic solar cells almost all electron-hole pairs generated at the donor-acceptor interface escape from their mutual coulomb potential remains to be a conceptual challenge. It has been argued that it is the excess energy dissipated in the course of electron or hole transfer at the interface that assists this escape process. The current work demonstrates that this concept is unnecessary to explain the field dependence of electron-hole dissociation. It is based upon the formalism developed by Arkhipov and co-workers as well as Baranovskii and co-workers. The key idea is that the binding energy of the dissociating "cold" charge-transfer state is reduced by delocalization of the hole along the polymer chain, quantified in terms of an "effective mass", as well as the fractional strength of dipoles existent at the interface in the dark. By covering a broad parameter space, we determine the conditions for efficient electron-hole dissociation. Spectroscopy of the charge-transfer state on bilayer solar cells as well as measurements of the field dependence of the dissociation yield over a broad temperature range support the theoretical predictions.

  7. Dissociated Vertical Deviation

    MedlinePlus

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  8. Combining ab initio quantum mechanics with a dipole-field model to describe acid dissociation reactions in water: first-principles free energy and entropy calculations.

    PubMed

    Maurer, Patrick; Iftimie, Radu

    2010-02-21

    We introduce a novel approach to compute dissociation free energy and entropy values in simulations that employ a density functional theory description of the acidic moiety and of the solvent. The approach consists of utilizing an alchemical transformation of a weak acid A-COOH into the strong acid B-COOH, which makes it practical to employ alchemical free energy perturbation methods in the context of ab initio molecular dynamics simulations. The present alchemical transformation circumvents the need to tackle changes in the total number of electrons and atoms by replacing the chemical residue responsible for the change in acidity with an easily tunable external effective potential. Our investigation demonstrates that (1) a simple but effective class of external potentials that control acidity changes in the acetic/trifluoroacetic acid series can be achieved by replacing the methyl and trifluoromethyl substituents by screened dipoles. Using this dipole-field/quantum-mechanics (DF/QM) approach one can predict gas-phase geometries, proton dissociation energies, total dipole moments, and water binding energies in good agreement with full-QM values. (2) The resulting alchemical perturbation calculations are stable and well converged and allow one to compute absolute pK(a) values whose accuracy is limited primarily by the exchange-correlation functional employed: H-COOH=2.5+/-0.6 (full-QM calculation), 3.7 (exp); F(3)C-COOH=0.4+/-0.6 (DF/QM calculation), 0.5 (exp); H(3)C-COOH=3.1+/-0.7 (DF/QM calculation), 4.7 (exp); 3) Our DF/QM model predicts that the difference in acidity between H-COOH and H(3)C-COOH is dominated by solvent entropy effects, in excellent agreement with experimental observations. The calculated difference between the dissociation energies of these acids is DeltaDelta(d)U=0.0+/-0.26 kcal/mol while the experimental value is 0.0+/-0.1 kcal/mol.

  9. Cognitive and dissociative manifestations in fibromyalgia.

    PubMed

    Leavitt, Frank; Katz, Robert S; Mills, Megan; Heard, Amy R

    2002-04-01

    Memory decline and mental confusion frequently complicate the clinical presentation of fibromyalgia; however, formal cognitive examination often does not support deterioration. This paradox was examined in the context of dissociation, a condition with many cognitive similarities. Dissociation refers to the separation of parts of experience from the mainstream of consciousness. A common example is highway hypnosis. Eighty-nine fibromyalgia (FM) patients and 64 other rheumatic disease patients were screened for memory decline and mental confusion using a questionnaire format. Pain, dissociation, affective distress, fatigue, sleep difficulty, and mental confusion were also assessed. Cognitive complaints (76.4%-43.8%) and dissociative symptoms (37.1%-1.9%) were overrepresented in patients with FM. Among FM patients with high dissociation, cognitive difficulties were reported by 95%; 100% of these cases reported that both memory and mental clarity were affected, a condition referred to as fibrofog. Dissociation in combination with fibrofog was associated with higher levels of FM symptom intensity and decreased mental well being. These findings suggest that dissociation may play a role in FM symptom amplification and may aid in comprehending the regularity of cognitive symptoms. Separating cases of fibrofog from cognitive conditions with actual brain damage is important. It may be prudent to add a test of dissociation as an adjunct to the evaluation of FM patients in cases of suspected fibrofog. Otherwise, test results may prove normal even in patients with disabling cognitive symptoms.

  10. Tailored noise waveform/collision-induced dissociation of ions stored in a linear ion trap combined with liquid chromatography/Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Vilkov, Andrey N; Bogdanov, Bogdan; Pasa-Tolić, Ljiljana; Prior, Dave C; Anderson, Gordon A; Masselon, Christophe D; Moore, Ronald J; Smith, Richard D

    2004-01-01

    A new collision-induced dissociation (CID) technique based on broadband tailored noise waveform (TNW) excitation of ions stored in a linear ion trap has been developed. In comparison with the conventional sustained off-resonance irradiation (SORI) CID method commonly used in Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), this MS/MS technique increases throughput by eliminating the long pump-down delay associated with gas introduction into the high vacuum ICR cell region. In addition, the TNW-CID method speeds spectrum acquisition since it does not require Fourier transformation, calculation of resonant frequencies and generation of the excitation waveforms. We demonstrate TNW-CID coupled with on-line capillary reverse-phase liquid chromatography separations for the identification of peptides. The experimental results are compared with data obtained using conventional quadrupole ion trap MS/MS and SORI-CID MS/MS in an ICR cell.

  11. Higher-energy Collision-activated Dissociation Without a Dedicated Collision Cell*

    PubMed Central

    McAlister, Graeme C.; Phanstiel, Douglas H.; Brumbaugh, Justin; Westphall, Michael S.; Coon, Joshua J.

    2011-01-01

    Beam-type collisional activation dissociation (HCD) offers many advantages over resonant excitation collision-activated dissociation, including improved identification of phosphorylated peptides and compatibility with isobaric tag-based quantitation (e.g. tandem mass tag (TMT) and iTRAQ). However, HCD typically requires specially designed and dedicated collision cells. Here we demonstrate that HCD can be performed in the ion injection pathway of a mass spectrometer with a standard atmospheric inlet (iHCD). Testing this method on complex peptide mixtures revealed similar identification rates to collision-activated dissociation (2883 versus 2730 IDs for iHCD/CAD, respectively) and precursor-product-conversion efficiency comparable to that achieved within a dedicated collision cell. Compared with pulsed-q dissociation, a quadrupole ion trap-based method that retains low-mass isobaric tag reporter ions, iHCD yielded isobaric tag for relative and absolute quantification reporter ions 10-fold more intense. This method involves no additional hardware and can theoretically be implemented on any mass spectrometer with an atmospheric inlet. PMID:21393638

  12. Products of Dissociative Recombination in the Ionosphere

    NASA Technical Reports Server (NTRS)

    Cosby, Philip

    1996-01-01

    SRI International undertook a novel experimental measurement of the product states formed by dissociative ro-combination (DR) of C2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and ro-vibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates.

  13. Imaging the molecular dynamics of dissociative electron attachment to water

    SciTech Connect

    Adaniya, Hidihito; Rudek, B.; Osipov, Timur; Haxton, Dan; Weber, Thorsten; Rescigno, Thomas N.; McCurdy, C.W.; Belkacem, Ali

    2009-10-19

    Momentum imaging experiments on dissociative electron attachment to the water molecule are combined with ab initio theoretical calculations of the angular dependence of the quantum mechanical amplitude for electron attachment to provide a detailed picture of the molecular dynamics of dissociation attachment via the two lowest energy Feshbach resonances. The combination of momentum imaging experiments and theory can reveal dissociation dynamics for which the axial recoil approximation breaks down and thus provides a powerful reaction microscope for DEA to polyatomics.

  14. Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree-Fock and Transition State Theory Approaches.

    PubMed

    Claudino, D; Gargano, R; Carvalho-Silva, Valter H; E Silva, Geraldo M; da Cunha, W F

    2016-07-21

    The present paper concludes our series of kinetics studies on the reactions involved in the complex mechanism of nitrogen trifluoride decomposition. Two other related reactions that, along with this mechanism, take part in an efficient boron nitride growth process are also investigated. We report results concerning two abstraction reactions, namely NF2 + N ⇄ 2NF and NF3 + NF ⇄ 2NF2, and two dissociations, N2F4 ⇄ 2NF2 and N2F3 ⇄ NF2 + NF. State-of-the-art electronic structure calculations at the CCSD(T)/cc-pVTZ level of theory were considered to determine geometries and frequencies of reactants, products, and transition states. Extrapolation of the energies to the complete basis set limit was used to obtain energies of all the species. We applied transition state theory to compute thermal rate constants including Wigner, Eckart, Bell, and deformed theory corrections in order to take tunneling effects into account. The obtained results are in good agreement with the experimental data available in the literature and are expected to provide a better phenomenological understanding of the NF3 decomposition role in the boron nitride growth for a wide range of temperature values. PMID:27355487

  15. Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree-Fock and Transition State Theory Approaches.

    PubMed

    Claudino, D; Gargano, R; Carvalho-Silva, Valter H; E Silva, Geraldo M; da Cunha, W F

    2016-07-21

    The present paper concludes our series of kinetics studies on the reactions involved in the complex mechanism of nitrogen trifluoride decomposition. Two other related reactions that, along with this mechanism, take part in an efficient boron nitride growth process are also investigated. We report results concerning two abstraction reactions, namely NF2 + N ⇄ 2NF and NF3 + NF ⇄ 2NF2, and two dissociations, N2F4 ⇄ 2NF2 and N2F3 ⇄ NF2 + NF. State-of-the-art electronic structure calculations at the CCSD(T)/cc-pVTZ level of theory were considered to determine geometries and frequencies of reactants, products, and transition states. Extrapolation of the energies to the complete basis set limit was used to obtain energies of all the species. We applied transition state theory to compute thermal rate constants including Wigner, Eckart, Bell, and deformed theory corrections in order to take tunneling effects into account. The obtained results are in good agreement with the experimental data available in the literature and are expected to provide a better phenomenological understanding of the NF3 decomposition role in the boron nitride growth for a wide range of temperature values.

  16. Electronic and nuclear structural snapshots in ligand dissociation and recombination processes of iron porphyrin in solution: a combined optical/X-ray approach.

    PubMed

    Mara, Michael W; Shelby, Megan; Stickrath, Andrew; Harpham, Mike; Huang, Jier; Zhang, Xiaoyi; Hoffman, Brian M; Chen, Lin X

    2013-11-14

    The photodissociation and recombination of CO and 1-methylimidazole (Im) from iron protoporphyrin IX (FePP-ImCO) dissolved in a 30% v/v aqueous solution of Im was studied using ultrafast optical transient absorption (TA) and X-ray transient absorption (XTA) spectroscopies. FePP-ImCO was shown to lose the CO ligand upon excitation at the Q bands, with 3.8 ps vibrational cooling and 21.6 ps intersystem crossing time constants derived from optical TA experiments, followed by ligation of a second Im on the nanosecond time scale. The penta-coordinate FePP-Im intermediate which forms following CO dissociation adopts a square pyramidal geometry with a "domed" iron center that is reminiscent of that formed upon loss of CO from carbonmonoxymyoglobin (MbCO). Unlike MbCO, which typically retains its newly generated penta-coordinated geometry until CO recombination, FePP can adopt a hexa-coordinate geometry by binding an additional Im ligand (FePP-(Im)2), allowing the porphyrin to exist in the low-spin electronic state even without the CO attached. The second Im ligand remains bound until CO recombination occurs with a time constant of 283 μs. The photodissociated states of FePP-ImCO and MbCO 100 ps after photoexcitation have similar iron site geometries, implying that the protein matrix in MbCO maintains minimum potential energy in the heme center despite the large-scale reorganization in the protein secondary and tertiary structure that arises from the dynamic active site/matrix interaction.

  17. A combined kick-out and dissociative diffusion mechanism of grown-in Be in InGaAs and InGaAsP. A new finite difference-Bairstow method for solution of the diffusion equations

    SciTech Connect

    Koumetz, Serge D. Martin, Patrick; Murray, Hugues

    2014-09-14

    Experimental results on the diffusion of grown-in beryllium (Be) in indium gallium arsenide (In{sub 0.53}Ga{sub 0.47}As) and indium gallium arsenide phosphide (In{sub 0.73}Ga{sub 0.27}As{sub 0.58}P{sub 0.42}) gas source molecular beam epitaxy alloys lattice-matched to indium phosphide (InP) can be successfully explained in terms of a combined kick-out and dissociative diffusion mechanism, involving neutral Be interstitials (Be{sub i}{sup 0}), singly positively charged gallium (Ga), indium (In) self-interstitials (I{sub III}{sup +}) and singly positively charged Ga, In vacancies (V{sub III}{sup +}). A new numerical method of solution to the system of diffusion equations, based on the finite difference approximations and Bairstow's method, is proposed.

  18. The dissociative bond.

    PubMed

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  19. The dissociative bond.

    PubMed

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other. PMID:23282044

  20. Combined photoelectron, collision-induced dissociation, and computational studies of parent and fragment anions of N-paranitrophenylsulfonylalanine and N-paranitrophenylalanine

    SciTech Connect

    Lambert, Jason; Chen, Jing; Buonaugurio, Angela; Bowen, Kit H. E-mail: kbowen@jhu.edu; Do-Thanh, Chi-Linh; Wang, Yilin; Best, Michael D.; Compton, R. N. E-mail: kbowen@jhu.edu; Sommerfeld, Thomas

    2013-12-14

    After synthesizing the compounds N-paranitrophenylsulfonylalanine (NPNPSA) and N-paranitrophenylalanine (NPNPA), the photoelectron spectrum of the valence anion of N-paranitrophenylsulfonylalanine (NPNPSA){sup −}, was measured and the collision-induced dissociation (CID) pathways of deprotonated N-paranitrophenylsulfonylalanine (NPNPSA-H){sup −} and deprotonated N-paranitrophenylalanine (NPNPA-H){sup −} were determined. Pertinent calculations were conducted to analyze both sets of experimental data. From the valence anion photoelectron spectrum of (NPNPSA){sup −}, the adiabatic electron affinity (AEA) of NPNPSA was determined to be 1.7 ± 0.1 eV, while the vertical detachment energy (VDE) of (NPNPSA){sup −} was found to be 2.3 ± 0.1 eV. Calculations for four low lying conformers of (NPNPSA){sup −} gave AEA values in the range of 1.6–2.1 eV and VDE values in the range of 2.0–2.4 eV. These calculations are in very good agreement with the experimental values. While the NPNPA anion (NPNPSA){sup −} was not observed experimentally it was studied computationally. The six low lying (NPNPSA){sup −} conformers were identified and calculated to have AEA values in the range of 0.7–1.2 eV and VDE values in the range of 0.9–1.6 eV. CID was used to study the fragmentation patterns of deprotonated NPNPA and deprotonated NPNPSA. Based on the CID data and calculations, the excess charge was located on the delocalized π-orbitals of the nitrobenzene moiety. This is made evident by the fact that the dominant fragments all contained the nitrobenzene moiety even though the parent anions used for the CID study were formed via deprotonation of the carboxylic acid. The dipole-bound anions of both molecules are studied theoretically using the results of previous studies on nitrobenzene as a reference.

  1. Generalised dissociative amnesia.

    PubMed

    Sengupta, S N; Jena, S; Saxena, S

    1993-12-01

    A case of generalised dissociative amnesia is presented, which illustrates several characteristic features of this uncommon condition. The case showed poor response to thiopentone interviews and in vivo cueing. Amnesia had persisted at six months follow up.

  2. Intelligent Albumin-MnO2 Nanoparticles as pH-/H2 O2 -Responsive Dissociable Nanocarriers to Modulate Tumor Hypoxia for Effective Combination Therapy.

    PubMed

    Chen, Qian; Feng, Liangzhu; Liu, Jingjing; Zhu, Wenwen; Dong, Ziliang; Wu, Yifan; Liu, Zhuang

    2016-09-01

    A unique type of pH/H2 O2 dual-responsive intelligent nanoscale delivery system based on albumin-coated MnO2 is presented, which is capable of modulating the tumor microenvironment (TME) by relieving hypoxia. Additionally, TME-responsive size changes enable effective intratumor diffusion. A highly effective combined photodynamic and chemotherapy is realized with these nanoparticles in a mouse tumor model. PMID:27283434

  3. Fast kinetics of calcium dissociation from calsequestrin.

    PubMed

    Beltrán, Marianela; Barrientos, Genaro; Hidalgo, Cecilia

    2006-01-01

    We measured the kinetics of calcium dissociation from calsequestrin in solution or forming part of isolated junctional sarcoplasmic reticulum membranes by mixing calsequestrin equilibrated with calcium with calcium-free solutions in a stopped-flow system. In parallel, we measured the kinetics of the intrinsic fluorescence changes that take place following calcium dissociation from calsequestrin. We found that at 25 degrees C calcium dissociation was 10-fold faster for calsequestrin attached to junctional membranes (k = 109 s(-1)) than in solution. These results imply that calcium dissociation from calsequestrin in vivo is not rate limiting during excitation-contraction coupling. In addition, we found that the intrinsic fluorescence decrease for calsequestrin in solution or forming part of junctional membranes was significantly slower than the rates of calcium dissociation. The kinetics of intrinsic fluorescence changes had two components for calsequestrin associated to junctional membranes and only one for calsequestrin in solution; the faster component was 8-fold faster (k = 54.1 s(-1)) than the slower component (k = 6.9 s(-1)), which had the same k value as for calsequestrin in solution. These combined results suggest that the presence of calsequestrin at high concentrations in a restricted space, such as when bound to the junctional membrane, accelerates calcium dissociation and the resulting structural changes, presumably as a result of cooperative molecular interactions. PMID:17106581

  4. Dissociation as complex adaptation.

    PubMed

    Sel, R

    1997-03-01

    In this article the general theory of complex adaptive systems, substantiated by non-linear dynamics, will be used to put the dissociative disorders into a theoretical framework and clarify their genesis and presentation. When a system is far out of equilibrium, dissipative structures may be formed ('order out of chaos', as Prigogine (1) has put it). These structures provide the starting point for further evolution and co-evolution of competing groups of functional schemata divided on a bifurcation surface. Complex adaptation is almost inevitable in a complicated system (such as the brain) driven by non-linear dynamics. Dissociation is thus regarded as a consequence of adaptation to a chaotic environment rich in contrasts. In a sufficiently complex environment a person with dissociative identity disorder is more adapted and thus more likely to occur than a 'normal' monopersonality individual.

  5. Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation.

    PubMed

    Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

    2016-06-22

    Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical variational transition state theory with small-curvature tunneling, combined with the Lindemann-Hinshelwood mechanism, to model the dissociation reaction of fluoroform (CHF3), which provides a definitive test for falloff modeling. Our predicted pressure-dependent thermal rate constants are in excellent agreement with experimental values over a wide range of pressures and temperatures. The present validation of our methodology, which is able to include variational transition state effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity, together with state-of-the-art reaction-path-based direct dynamics calculations, is important because the method is less empirical than models routinely used for generating full mechanisms, while also being simpler in key respects than full master equation treatments and the full reduced falloff curve and modified strong collision methods of Troe. PMID:27273734

  6. Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation.

    PubMed

    Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

    2016-06-22

    Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical variational transition state theory with small-curvature tunneling, combined with the Lindemann-Hinshelwood mechanism, to model the dissociation reaction of fluoroform (CHF3), which provides a definitive test for falloff modeling. Our predicted pressure-dependent thermal rate constants are in excellent agreement with experimental values over a wide range of pressures and temperatures. The present validation of our methodology, which is able to include variational transition state effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity, together with state-of-the-art reaction-path-based direct dynamics calculations, is important because the method is less empirical than models routinely used for generating full mechanisms, while also being simpler in key respects than full master equation treatments and the full reduced falloff curve and modified strong collision methods of Troe.

  7. Dissociative Identity Disorder

    ERIC Educational Resources Information Center

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  8. Dissociation: the clinical realities.

    PubMed

    Frankel, F H

    1996-07-01

    An attempt was made by the authors of DSM-III to restrict its focus to the experimental, the observable, and the measurable. The intention was to free the nosology from the influence of unproven theories, and the philosophy was driven largely by the importance of research being able to identify diagnostic categories to facilitate the study of homogeneous groups. So it is of interest that the authors accepted dissociation-an ambiguous event linked to an explicit theoretical concept that had been introduced by Janet-as the basis for classification of clinical presentations that were formerly included under the rubric of hysteria, a similarly unclear category. Since DSM-III, there have been an increasing number of reports of dissociative experiences and dissociative identity disorder (formerly known as multiple personality disorder), but neither of these clinical presentations seems able to withstand the concern that it is dramatically influenced by environmental cues, e.g., the expectations of the therapist. Thus, a restricted phenomenological perspective does not fully appreciate the distorting potential of suggestibility and imagination on the nature of the emerging clinical picture. These factors might well have contributed to and laid the conceptual groundwork for the growth in the number of reports of dissociation.

  9. Dissociation and psychosis in dissociative identity disorder and schizophrenia.

    PubMed

    Laddis, Andreas; Dell, Paul F

    2012-01-01

    Dissociative symptoms, first-rank symptoms of schizophrenia, and delusions were assessed in 40 schizophrenia patients and 40 dissociative identity disorder (DID) patients with the Multidimensional Inventory of Dissociation (MID). Schizophrenia patients were diagnosed with the Structured Clinical Interview for the DSM-IV Axis I Disorders; DID patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised. DID patients obtained significantly (a) higher dissociation scores; (b) higher passive-influence scores (first-rank symptoms); and (c) higher scores on scales that measure child voices, angry voices, persecutory voices, voices arguing, and voices commenting. Schizophrenia patients obtained significantly higher delusion scores than did DID patients. What is odd is that the dissociation scores of schizophrenia patients were unrelated to their reports of childhood maltreatment. Multiple regression analyses indicated that 81% of the variance in DID patients' dissociation scores was predicted by the MID's Ego-Alien Experiences Scale, whereas 92% of the variance in schizophrenia patients' dissociation scores was predicted by the MID's Voices Scale. We propose that schizophrenia patients' responses to the MID do not index the same pathology as do the responses of DID patients. We argue that neither phenomenological definitions of dissociation nor the current generation of dissociation instruments (which are uniformly phenomenological in nature) can distinguish between the dissociative phenomena of DID and what we suspect are just the dissociation-like phenomena of schizophrenia.

  10. Pathological Dissociation as Measured by the Child Dissociative Checklist

    ERIC Educational Resources Information Center

    Wherry, Jeffrey N.; Neil, Debra A.; Taylor, Tamara N.

    2009-01-01

    The component structure of the Child Dissociative Checklist was examined among abused children. A factor described as pathological dissociation emerged that was predicted by participants being male. There also were differences in pathological dissociation between groups of sexually abused and physically abused children. Replication of this factor…

  11. Free energy calculations of gramicidin dimer dissociation.

    PubMed

    Wanasundara, Surajith N; Krishnamurthy, Vikram; Chung, Shin-Ho

    2011-11-24

    Molecular dynamics simulations, combined with umbrella sampling, is used to study how gramicidin A (gA) dimers dissociate in the lipid bilayer. The potential of mean force and intermolecular potential energy are computed as functions of the distance between center of masses of the two gA monomers in two directions of separation: parallel to the bilayer surface and parallel to the membrane normal. Results from this study show that the dissociation of gA dimers occurs via lateral displacement of gA monomers followed by tilting of dimers with respect to the lipid bilayer normal. It is found that the dissociation energy of gA dimers in the dimyristoylphosphatidylcholine bilayer is 14 kcal mol(-1) (~22 kT), which is approximately equal to the energy of breaking six intermolecular hydrogen bonds that stabilize the gA channel dimer.

  12. Traumatic Dissociation as a Predictor of Posttraumatic Stress Disorder in South African Female Rape Survivors

    PubMed Central

    Nöthling, Jani; Lammers, Kees; Martin, Lindi; Seedat, Soraya

    2015-01-01

    Abstract Women survivors of rape are at an increased risk for posttraumatic stress disorder (PTSD). Traumatic dissociation has been identified as a precursor of PTSD. This study assessed the predictive potential of traumatic dissociation in PTSD and depression development. The study followed a longitudinal, prospective design. Ninety-seven female rape survivors were recruited from 2 clinics in Cape Town, South Africa. Clinical interviews and symptom status assessments of the participants were completed to measure dissociation, childhood traumas, resilience, depression, and PTSD. Traumatic dissociation was a significant predictor of PTSD and depression. The linear combination of prior dissociation, current dissociation, and resilience significantly explained 20.7% of the variance in PTSD. Dissociation mediated the relationship between resilience and PTSD. As traumatic dissociation significantly predicts PTSD, its early identification and management may reduce the risk of developing PTSD. Interventions focused on promoting resilience may also be successful in reducing the risk of dissociation following rape. PMID:25906104

  13. Traumatic dissociation as a predictor of posttraumatic stress disorder in South African female rape survivors.

    PubMed

    Nöthling, Jani; Lammers, Kees; Martin, Lindi; Seedat, Soraya

    2015-04-01

    Women survivors of rape are at an increased risk for posttraumatic stress disorder (PTSD). Traumatic dissociation has been identified as a precursor of PTSD. This study assessed the predictive potential of traumatic dissociation in PTSD and depression development.The study followed a longitudinal, prospective design. Ninety-seven female rape survivors were recruited from 2 clinics in Cape Town, South Africa. Clinical interviews and symptom status assessments of the participants were completed to measure dissociation, childhood traumas, resilience, depression, and PTSD.Traumatic dissociation was a significant predictor of PTSD and depression. The linear combination of prior dissociation, current dissociation, and resilience significantly explained 20.7% of the variance in PTSD. Dissociation mediated the relationship between resilience and PTSD.As traumatic dissociation significantly predicts PTSD, its early identification and management may reduce the risk of developing PTSD. Interventions focused on promoting resilience may also be successful in reducing the risk of dissociation following rape.

  14. Three dimensions of dissociative amnesia.

    PubMed

    Dell, Paul F

    2013-01-01

    Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders. PMID:23282045

  15. Three dimensions of dissociative amnesia.

    PubMed

    Dell, Paul F

    2013-01-01

    Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders.

  16. Dissociative ionization of biomolecules

    NASA Astrophysics Data System (ADS)

    Huo, Winifred

    2004-09-01

    Dissociative ionization (DI) by electron impact plays a role in many different applications, including low-temperature plasma processing, the study of space and astrophysical plasmas, and the study of biological damages by high-energy radiation. In the present study, our goal is to understand the health hazard to humans from exposure to radiation during an extended space flight. DI by secondary electrons can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. The theoretical model employed makes use of the fact that electronic motion is much faster than nuclear motion, allowing DI to be treated as a two-step process. The first step is electron-impact ionization resulting in a dissociative state of the molecular ion with the same geometry as the neutral molecule. In the second step the ion relaxes from the initial geometry and undergoes unimolecular dissociation. Thus the DI cross section is given by the product of the ionization cross section and the dissociation probability. For the ionization process we use the improved binary-encounter dipole (iBED) model. For unimolecular dissociation, we use the multiconfigurational self-consistent field (MCSCF) method to determine the minimum energy pathways to possible product channels. This model has been applied to study the DI of H_2O, NH_3, and CH_4, and the results are in good agreement with experiment. The DI from the low-lying channels of benzene has also been studied and the dissociation products are compared with photoionization measurements. The DI of the DNA bases guanine and cytosine are then discussed. Of the four DNA bases, guanine has the largest ionization cross section and cytosine has the smallest. The guanine radical cation is considered to be one of the precursors to the primary, direct-type lesions formed in DNA when it is irradiated. Comparison of DI products of guanine and cytosine will be made to understand the differences in

  17. [A dissociative patient].

    PubMed

    de Jongh, A; Abkhezr, S; Broers, D L M

    2009-08-01

    A 45-year-old woman attended a centre for special dental care. Initially, it seemed that the patient suffered from an extreme form of dental anxiety. However, the fact that she displayed 'dissociations' suggested that she had a severe psychiatric disorder, in this case Dissociative Identity Disorder. The key feature of this condition is a dysfunction of the normal integrative functions of identity, memory and consciousness. In such instances it is recommended to contact a psychologist or psychiatrist and the referring care provider to consider the consequences of the psychiatric condition regarding informed consent, treatment plan and actual treatment. Because it was not likely that the patient would respond to an intervention specifically aimed to reduce anxiety in the dental setting, dental treatment under general anesthesia was the best suited option.

  18. Dissociation and psychotic symptoms.

    PubMed

    Steingard, S; Frankel, F H

    1985-08-01

    The literature on hysterical or brief reactive psychosis reflects great diversity both in clinical description and theoretical formulation. The authors describe the case of a 17-year-old girl who presented with a diagnosis of bipolar affective disorder, rapid cycling type, but who, in fact, was experiencing dissociative episodes manifested as psychotic states. The patient's successful treatment with hypnosis is described, along with the clinical and theoretical implications of the case.

  19. Controllable dissociations of PH3 molecules on Si(001)

    NASA Astrophysics Data System (ADS)

    Liu, Qin; Lei, Yanhua; Shao, Xiji; Ming, Fangfei; Xu, Hu; Wang, Kedong; Xiao, Xudong

    2016-04-01

    We demonstrate for the first time to our knowledge that controllable dissociation of PH3 adsorption products PH x (x = 2, 1) can be realized by STM (scanning tunneling microscope) manipulation techniques at room temperature. Five dissociative products and their geometric structures are identified via combining STM experiments and first-principle calculations and simulations. In total we realize nine kinds of controllable dissociations by applying a voltage pulse among the PH3-related structures on Si(001). The dissociation rates of the five most common reactions are measured by the I-t spectrum method as a function of voltage. The suddenly increased dissociation rate at 3.3 V indicates a transition from multivibrational excitation to single-step excitation induced by inelastic tunneling electrons. Our studies prove that selectively breaking the chemical bonds of a single molecule on semiconductor surface by STM manipulation technique is feasible.

  20. Recurrent dissociative fugue.

    PubMed

    Mamarde, Abhishek; Navkhare, Praveen; Singam, Amrita; Kanoje, Akash

    2013-10-01

    Dissociative fugue is a rarely reported diagnostic entity. It is one of the least understood and yet clinically one of the most fascinating disorders in mental health. Here, we describe a case of fugue in a 32-year-old man who was brought to mental hospital with complete loss of memory for events pertaining to identity of self. This case illustrates the nature of presentation in hospital setting like mental hospital and effort taken to reintegrate his identity and reunite with his family. PMID:24379504

  1. Recurrent dissociative fugue.

    PubMed

    Mamarde, Abhishek; Navkhare, Praveen; Singam, Amrita; Kanoje, Akash

    2013-10-01

    Dissociative fugue is a rarely reported diagnostic entity. It is one of the least understood and yet clinically one of the most fascinating disorders in mental health. Here, we describe a case of fugue in a 32-year-old man who was brought to mental hospital with complete loss of memory for events pertaining to identity of self. This case illustrates the nature of presentation in hospital setting like mental hospital and effort taken to reintegrate his identity and reunite with his family.

  2. Recurrent Dissociative Fugue

    PubMed Central

    Mamarde, Abhishek; Navkhare, Praveen; Singam, Amrita; Kanoje, Akash

    2013-01-01

    Dissociative fugue is a rarely reported diagnostic entity. It is one of the least understood and yet clinically one of the most fascinating disorders in mental health. Here, we describe a case of fugue in a 32-year-old man who was brought to mental hospital with complete loss of memory for events pertaining to identity of self. This case illustrates the nature of presentation in hospital setting like mental hospital and effort taken to reintegrate his identity and reunite with his family. PMID:24379504

  3. THE DISSOCIATIVE TURN IN PSYCHOANALYSIS.

    PubMed

    Itzkowitz, Sheldon

    2015-06-01

    In his response to the Roundtable Discussions on what is effective in psychoanalytic psychotherapy, the author focuses on the renewed interest in the concept of dissociation that began to emerge toward the end of the 20th century. A contemporary psychoanalytic position informed by the impact of developmental trauma has led to an understanding of and interest in the dissociative mind. The actuality of trauma during infancy and early childhood is recognized as a key factor leading to the emergence of dissociative processes, the potential dissociative structuring of the mind, and mind being characterized by multiple, discontinuous, centers of consciousness. The therapeutic goal in the psychoanalytic work with fragmented patients is to establish communication and understanding between the dissociated self-states. The author offers two brief clinical examples of working with dissociated self-states.

  4. Dissociative state and competence.

    PubMed

    Lin, Yu-Ju; Hsieh, Ming-Hsien; Liu, Shi-Kai

    2007-10-01

    This report presents the results of forensic evaluation of the civil competence of a case of alleged dissociative identity disorder (DID) and discusses whether such dissociative states substantially jeopardize civil competence. A 40-year-old woman claimed that she had had many personalities since her college days. From the age of 37 to 40, she shopped excessively, which left her with millions of dollars of debt. She ascribed her shopping to a certain identity state, over which she had no control. (In this article, we use the term identity state to replace personality as an objective description of a mental state.) She thus raised the petition of civil incompetence. During the forensic evaluation, it was found that the identity states were relatively stable and mutually aware of each other. The switch into another identity state was sometimes under voluntary control. The subject showed consistency and continuity in behavioral patterns across the different identity states, and no matter which identity state she was in, there was no evidence of impairment in her factual knowledge of social situations and her capacity for managing personal affairs. We hence concluded that she was civilly competent despite the claimed DID. Considering that the existence and diagnosis of DID are still under dispute and a diagnosis of DID alone is not sufficient to interdict a persons civil right, important clinical and forensic issues remain to be answered.

  5. Dissociative Electron Attachment

    NASA Astrophysics Data System (ADS)

    Arreola, Esmeralda; Esmeralda Arreola Collaboration; Leigh Hargreaves Collaboration

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  6. DIFFRACTION DISSOCIATION - 50 YEARS LATER.

    SciTech Connect

    WHITE, S.N.

    2005-04-27

    The field of Diffraction Dissociation, which is the subject of this workshop, began 50 years ago with the analysis of deuteron stripping in low energy collisions with nuclei. We return to the subject in a modern context- deuteron dissociation in {radical}s{sub NN} = 200 GeV d-Au collisions recorded during the 2003 RHIC run in the PHENIX experiment. At RHIC energy, d {yields} n+p proceeds predominantly (90%) through Electromagnetic Dissociation and the remaining fraction via the hadronic shadowing described by Glauber. Since the dissociation cross section has a small theoretical error we adopt this process to normalize other cross sections measured in RHIC.

  7. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly

    PubMed Central

    Ram, Dushad; Ashoka, H. G; Gowdappa, Basavnna

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed. PMID:26286620

  8. Dissociative States and Neural Complexity

    ERIC Educational Resources Information Center

    Bob, Petr; Svetlak, Miroslav

    2011-01-01

    Recent findings indicate that neural mechanisms of consciousness are related to integration of distributed neural assemblies. This neural integration is particularly vulnerable to past stressful experiences that can lead to disintegration and dissociation of consciousness. These findings suggest that dissociation could be described as a level of…

  9. Dissociation Patterns in Evolving Populations

    NASA Astrophysics Data System (ADS)

    Moreno, F. J.; Hernández, J. A.; Sánchez, F.

    2011-09-01

    The recent explosion and availability of mobility based technologies such as geographic information systems, cell phones equipped with built-in GPS, among others, are a valuable source of spatio-temporal data. However, only recently there have been works focused on identifying movement patterns in groups of moving entities. We focus on a particular movement pattern: dissociation. A dissociation pattern occurs when an entity that was once associated to a population, eventually separated from it and subsequently reintegrated it again. The backwarding and forwarding patterns are a type of dissociation where an entity stays behind or ahead of another entity, respectively. Dissociation really is a diversity generator, so instead avoiding it, taking advantage could be better to prevent premature convergence in evolutionary algorithms. In this work, we present formal mathematical definitions for these patterns. A discussion of how to use dissociation patterns as a mean to preserve diversity in evolutionary algorithms is also shown.

  10. The dissociative disorders. Rarely considered and underdiagnosed.

    PubMed

    Coons, P M

    1998-09-01

    A wide variety of dissociative disorders, including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and various forms of dissociative disorder not otherwise specified. In many instances, these disorders are either underdiagnosed or misdiagnosed secondary to the clinician's mistaken belief that dissociative disorders are rare. Recent research shows that dissociative disorders may comprise 5% to 10% of psychiatric populations. This article reviews the epidemiology and clinical symptomatology of these disorders. In addition, various screening and diagnostic instruments, such as the DES, Structured Clinical Interview for Dissociative Disorders, and MMPI, are discussed.

  11. The Linkage Between Oxygenation and Subunit Dissociation in Human Hemoglobin

    PubMed Central

    Ackers, Gary K.; Halvorson, Herbert R.

    1974-01-01

    The use of subunit dissociation as a means of probing intersubunit contact energy changes which accompany cooperative ligand binding has been studied for the case of human hemoglobin. An analysis is presented delineating the information that can be obtained from the linkage relationships between ligand binding and subunit dissociation of hemoglobin tetramers into dimers. The analysis defines (a) the variation of the saturation function, Ȳ, with total protein concentration, (b) the variation of the subunit dissociation constant xK2 with ligand concentration (X) and (c) the correlations between changes in dimer-dimer contact energy and the sequential ligand binding steps. Sensitivity of the linkage function has been explored by numerical simulation. It is shown that subunit dissociation may appreciably affect oxygenation curves under usual conditions of measurement and that relying solely on either xK2 or Ȳ may lead to incorrect picutres of the energetics, whereas the combination defines the system much more exactly. PMID:4530985

  12. Are major dissociative disorders characterized by a qualitatively different kind of dissociation?

    PubMed

    Rodewald, Frauke; Dell, Paul F; Wilhelm-Gossling, Claudia; Gast, Ursula

    2011-01-01

    A total of 66 patients with a major dissociative disorder, 54 patients with nondissociative disorders, and 30 nonclinical controls were administered the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised, the Dissociative Experiences Scale, the Multidimensional Inventory of Dissociation, and the Symptom Checklist 90-Revised. Dissociative patients reported significantly more dissociative and nondissociative symptoms than did nondissociative patients and nonclinical controls. When general psychopathology was controlled, the dissociation scores of dissociative patients were still significantly higher than those of both other groups, whereas the dissociation scores of nondissociative patients and nonclinical controls no longer differed. These findings appear to be congruent with a typological model of dissociation that distinguishes between 2 qualitatively different kinds of dissociation. Specifically, the results of this study suggest that the dissociation that occurs in major dissociative disorders (i.e., dissociative identity disorder [DID] and dissociative disorder not otherwise specified, Type 1 [DDNOS-1]) is qualitatively different from the dissociation that occurs in persons who do not have a dissociative disorder. In contrast to previous research, the dissociation of persons who do not have a dissociative disorder is not limited to absorption; it covers a much wider range of phenomena. The authors hypothesize that different mechanisms produce the dissociation of persons with DID and DDNOS-1 as opposed to the dissociation of persons who do not have a dissociative disorder.

  13. Recurrent Episodes of Dissociative Fugue

    PubMed Central

    Angothu, Hareesh; Pabbathi, Lokeswar Reddy

    2016-01-01

    Dissociative fugue is rare entity to encounter with possible differentials of epilepsy and malingering. It is one of the dissociative disorders rarely seen in clinical practice more often because of the short lasting nature of this condition. This might also be because of organized travel of the individuals during the episodes and return to their families after the recovery from episodes. This is a case description of a patient who has experienced total three episodes of dissociative fugue. The patient has presented during the third episode and two prior episodes were diagnosed as fugue episodes retrospectively based on the history. Planned travel in this case by the patient to a distant location was prevented because of early diagnosis and constant vigilance till the recovery. As in this case, it may be more likely that persons with Dissociative fugue may develop similar episodes if they encounter exceptional perceived stress. However, such conclusions may require follow-up studies. PMID:27114633

  14. Global functioning and disability in dissociative disorders.

    PubMed

    Mueller-Pfeiffer, Christoph; Rufibach, Kaspar; Perron, Noelle; Wyss, Daniela; Kuenzler, Cornelia; Prezewowsky, Cornelia; Pitman, Roger K; Rufer, Michael

    2012-12-30

    Dissociative disorders are frequent comorbid conditions of other mental disorders. Yet, there is controversy about their clinical relevance, and little systematic research has been done on how they influence global functioning. Outpatients and day care patients (N=160) of several psychiatric units in Switzerland were assessed with the Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders (DSM)-IV Axis I Disorders, Structured Clinical Interview for DSM-IV Dissociative Disorders, Global Assessment of Functioning Scale, and World Health Organization Disability Assessment Schedule-II. The association between subjects with a dissociative disorder (N=30) and functional impairment after accounting for non-dissociative axis I disorders was evaluated by linear regression models. We found a proportion of 18.8% dissociative disorders (dissociative amnesia=0%, dissociative fugue=0.6%, depersonalization disorder=4.4%, dissociative identity disorder=7.5%, dissociative disorder-not-otherwise-specified=6.3%) across treatment settings. Adjusted for other axis I disorders, subjects with a comorbid dissociative identity disorder or dissociative disorder-not-otherwise-specified had a median global assessment of functioning score that was 0.86 and 0.88 times, respectively, the score of subjects without a comorbid dissociative disorder. These findings support the hypothesis that complex dissociative disorders, i.e., dissociative identity disorder and dissociative disorder-not-otherwise-specified, contribute to functional impairment above and beyond the impact of co-existing non-dissociative axis I disorders, and that they qualify as "serious mental illness".

  15. Evaluation of a Novel Approach for Peptide Sequencing: Laser-induced Acoustic Desorption Combined with P(OCH3)2+ Chemical Ionization and Collision-activated Dissociation in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

    PubMed Central

    Somuramasami, Jayalakshmi; Kenttämaa, Hilkka I.

    2007-01-01

    A novel mass spectrometric method has been developed for obtaining sequence information on small peptides. The peptides are desorbed as intact neutral molecules into a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) by means of laser-induced acoustic desorption (LIAD). Reactions of the neutral peptides with the dimethoxyphosphenium ion, P(OCH3)2+, occur predominantly by addition of the peptide to P(OCH3)2+ followed by the loss of two methanol molecules, thus yielding product ions with the composition (peptide + P − 2H)+. Upon sustained off-resonance irradiation for collision-activated dissociation (SORI-CAD), the (peptide + P − 2H)+ ions undergo successive losses of CO and NH = CHR or H2O, CO, and NH = CHR to yield sequence-related fragment ions in addition to the regular an- and bn-type ions. Under the same conditions, SORI-CAD of the analogous protonated peptides predominantly yields the regular an- and bn-type ions. The mechanisms of the reactions of peptides with P(OCH3)2+ and the dissociation of the (peptide + P − 2H)+ ions were examined by using model peptides and molecular orbital calculations. PMID:17157527

  16. Dissociation Energies of Sulfur-Centered Hydrogen-Bonded Complexes.

    PubMed

    Ghosh, Sanat; Bhattacharyya, Surjendu; Wategaonkar, Sanjay

    2015-11-01

    In this work we have determined dissociation energies of O-H···S hydrogen bond in the H2S complexes of various phenol derivatives using 2-color-2-photon photofragmentation spectroscopy in combination with zero kinetic energy photoelectron (ZEKE-PE) spectroscopy. This is the first report of direct determination of dissociation energy of O-H···S hydrogen bond. The ZEKE-PE spectra of the complexes revealed a long progression in the intermolecular stretching mode with significant anharmonicity. Using the anharmonicity information and experimentally determined dissociation energy, we also validated Birge-Sponer (B-S) extrapolation method, which is an approximate method to estimate dissociation energy. Experimentally determined dissociation energies were compared with a variety of ab initio calculations. One of the important findings is that ωB97X-D functional, which is a dispersion corrected DFT functional, was able to predict the dissociation energies in both the cationic as well as the ground electronic state very well for almost every case.

  17. Dissociative experiences and dissociative minds: Exploring a nomological network of dissociative functioning.

    PubMed

    Schimmenti, Adriano

    2016-01-01

    In this study, the psychometric properties of the Dissociative Experiences Scale-II (DES-II) were tested in a sample of Italian adults, and a nomological network of dissociative functioning based on current psychodynamic research was examined. A total of 794 participants (55% females) ranging in age from 18 to 64 completed the DES-II and other measures of theory of mind, alexithymia, attachment style, and empathy. The Italian translation of the DES-II showed high internal consistency, adequate item-to-scale homogeneity, and good split-half reliability. A single-factor solution including the 8 items of pathological dissociation (DES-T) adequately fit the data. Participants who reported higher levels of dissociative experiences showed significantly lower scores on theory of mind and empathy than other participants. They also showed significantly higher scores on alexithymia, preoccupied attachment, and fearful attachment. Results of the study support the view that people who suffer from severe dissociative experiences may also have difficulties mentalizing and regulating affects and that they may feel uncomfortable in close relationships because they have a negative view of the self. This can inform clinical work with dissociative individuals, who could benefit from therapies that consider their potential problems with mentalization, empathy, affect regulation, and attachment.

  18. Subunit dissociation in fish hemoglobins.

    PubMed

    Edelstein, S J; McEwen, B; Gibson, Q H

    1976-12-10

    The tetramer-dimer dissociation equilibria (K 4,2) of several fish hemoglobins have been examined by sedimentation velocity measurements with a scanner-computer system for the ultracentrifuge and by flash photolysis measurements using rapid kinetic methods. Samples studied in detail included hemoglobins from a marine teleost, Brevoortia tyrannus (common name, menhaden); a fresh water teleost, Cyprinus carpio, (common name, carp); and an elasmobranch Prionace glauca (common name, blue shark). For all three species in the CO form at pH 7, in 0.1 M phosphate buffer, sedimentation coefficients of 4.3 S (typical of tetrameric hemoglobin) are observed in the micromolar concentration range. In contrast, mammalian hemoglobins dissociate appreciably to dimers under these conditions. The inability to detect dissociation in three fish hemoglobins at the lowest concentrations examined indicates that K 4,2 must have a value of 10(-8) M or less. In flash photolysis experiments on very dilute solutions in long path length cells, two kinetic components were detected with their proportions varying as expected for an equilibrium between tetramers (the slower component) and dimers (the faster component); values of K 4,2 for the three fish hemoglobins in the range 10(-9) to 10(-8) M were calculated from these data. Thus, the values of K 4,2 for liganded forms of the fish hemoglobins appear to be midway between the value for liganded human hemoglobin (K 4,2 approximately 10(-6) M) and unliganded human hemoglobin (K 4,2 approximately 10(-12) M). This conclusion is supported by measurements on solutions containing guanidine hydrochloride to enhance the degree of dissociation. All three fish hemoglobins are appreciably dissociated at guanidine concentrations of about 0.8 M, which is roughly midway between the guanidine concentrations needed to cause comparable dissociation of liganded human hemoglobin (about 0.4 M) and unliganded human hemoglobin (about 1.6 M). Kinetic measurements on

  19. Entropy and volume change of dissociation in tobacco mosaic virus probed by high pressure.

    PubMed

    Bispo, Jose A C; Bonafe, Carlos F S; Joekes, Ines; Martinez, Ernesto A; Carvalho, Giovani B M; Norberto, Douglas R

    2012-12-27

    Virus dissociation and inactivation by high pressure have been extensively studied in recent decades. Pressure-induced dissociation of viral particles involves a reduction in the Gibbs free energy of dissociation and a negative change in volume. In this work, we investigated the combined effect of high pressure and temperature on the dissociation of tobacco mosaic virus (TMV). We assumed the presence of two states of TMV with different tendencies to dissociate. Thus one form presents a low tendency (L) and the other a high tendency (H) to dissociate. Based on the model described here, the L-H transition was favored by an increase in pressure and a decrease in temperature. The volume change of dissociation was pressure- and temperature-dependent, with a highly negative value of -80 mL/mol being recorded at 0 °C and atmospheric pressure. The entropy and enthalpy of dissociation were very temperature- and pressure-dependent, with values of entropy of 450 to -1300 kJ/mol and values of enthalpy of 5.5 × 10(4) to 2.4 × 10(4) kJ/mol. The dissociation of TMV was enthalpy-driven at all temperatures and pressures investigated. Based on these findings, we conclude that the model presented allows accurate predictions of viral dissociation behavior in different experimental conditions. PMID:23205955

  20. Dissociative symptomatology in children and adolescents as displayed on psychological testing.

    PubMed

    Silberg, J L

    1998-12-01

    The purpose of this study was to investigate psychological testing features of children and adolescents with dissociative disorder diagnoses to provide diagnostic information that might facilitate early intervention. The psychological testing protocols of 30 children diagnosed with dissociative disorders were compared with the testing protocols of 30 consecutive admissions to the Sheppard Pratt Hospital who did not receive a dissociative identity disorder (DID; formerly termed multiple personality disorder) or dissociative disorder not otherwise specified (DDNOS) diagnosis. A rater, blind to the diagnosis, scored these protocols for the presence or absence of behavioral and testing response variables hypothesized to discriminate between the dissociative patients and the mixed group of other diagnoses. Behavioral features significantly more common in the dissociative group included forgetting, staring, unusual motor behaviors, dramatic fluctuations, fearful and angry reactions to stimuli, physical complaints during testing, and expressions of internal conflict. Significant indications of dissociation in the test responses included images of multiplicity, malevolent religiosity, dissociative coping, depersonalized imagery, emotional confusion, extreme dichotomization, images of mutilation and torture, and magical transformation. A combination of these behavioral and response variables was able to select 93% of the dissociative sample. These results add support to the discriminant validity of DID and DDNOS as diagnostic categories in childhood and provide clinical information that may be useful for early diagnosis of traumatized children with dissociative pathology.

  1. Multiphoton dissociative ionization of CS+

    NASA Astrophysics Data System (ADS)

    Rajput, Jyoti; Jochim, Bethany; Zohrabi, M.; Betsch, K. J.; Ablikim, U.; Berry, Ben; Severt, T.; Summers, A. M.; Armstrong, G. S. J.; Esry, B. D.; Carnes, K. D.; Ben-Itzhak, I.

    2015-05-01

    We have studied the dissociative photoionization of a CS+ molecular ion beam in the strong-field regime using <50 fs IR laser pulses (λ ~ 790 nm) from a 10 kHz, ~2 mJ (per pulse) Ti:Sapphire laser system. A coincidence three-dimensional momentum imaging method was used to measure all ions and neutrals formed during this multiphoton process. Two prominent channels were observed: charge-symmetric dissociation, yielding C+ + S+, and charge-asymmetric dissociation, yielding C + S2+. The differences between these two channels with reference to their relative production probability, energetics, and angular distributions is the focus of this work. This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy. BJ is also supported by DOE-SCGF (DE-AC05-06OR23100).

  2. Dissociative Electron Attachment to Carbon Dioxide via the 8.2 eV Feshbach resonance

    SciTech Connect

    Slaughter, Dan; Adaniya, Hidihito; Rescigno, Tom; Haxton, Dan; Orel, Ann; McCurdy, Bill; Belkacem, Ali

    2011-08-17

    Momentum imaging experiments on dissociative electron attachment (DEA) to CO{sub 2} are combined with the results of ab initio calculations to provide a detailed and consistent picture of the dissociation dynamics through the 8.2 eV resonance, which is the major channel for DEA in CO{sub 2}. The present study resolves several puzzling misconceptions about this system.

  3. [Dissociative identity disorder or schizophrenia?].

    PubMed

    Tschöke, S; Steinert, T

    2010-01-01

    We present a case of dissociative identity disorder in which Schneiderian first rank symptoms were present besides of various states of consciousness. Thus the diagnosis of schizophrenia had to be considered. Formally, the symptoms met ICD-10 criteria for schizophrenia. However, taking into account the lack of formal thought disorder and of negative symptoms as well as a typical history of severe and prolonged traumatisation, we did not diagnose a co-morbid schizophrenic disorder. There is good evidence for the existence of psychotic symptoms among patients with dissociative disorders. However, in clinical practice this differential diagnosis is rarely considered.

  4. [Traditional and modern views of dissociation].

    PubMed

    Merza, Katalin; Kuritárné Szabó, Ildikó

    2012-01-01

    Dissociation is a failure to integrate aspects of identity, memory, perception, and consciousness. Dissociation is conceptualized as a dimensional process existing along a continuum from normal and relatively common dissociative experiences to severe and clinically relevant forms. There is a growing body of clinical and empirical evidence that dissociation may occur especially as a defense during trauma. In case of traumatic events dissociation considered as an attempt to maintain mental control just as physical control is lost. Dissociation can be either a symptom of some complex mental disorder or a distinct clinical entity categorized among dissociative and somatoform disorders in DSM-IV. The article describes the conceptual issues of dissociation and presents a new classification by Nijenhuis where the so-called somatoform dissociative symptoms are included as well in the list of dissociative symptoms. Finally, this paper summarizes the measures of dissociative phenomena and the cognitive-behavioral approaches of dissociation, and highlights the main features of the new structural dissociation model.

  5. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    NASA Astrophysics Data System (ADS)

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  6. The return of dissociation as absence within absence.

    PubMed

    Gurevich, Hayuta

    2014-12-01

    My aim is to translate Ferenczi's central concepts of the intrapsychic impact and imprint of early developmental trauma into both revived and contemporary conceptualizations. The concept of dissociation was renounced by Freud, yet it is returning as a cornerstone of recent trauma theories. Ferenczi used the concept of "repression," but used it in the sense of an intrapsychic imprint of early external trauma that fragments consciousness, that is, as dissociation. Furthermore, early trauma is double: an absence of protection that threatens existence of the self, combined with an absence of attachment and of recognition of this threat and terror; thus it is an absence-within-absence. This contemporary conceptualization entails a widening of the intrapsychic realm to include an intersubjective one, and regards dissociation as a unique and complex intrapsychic absence, which is a negative of the external absence-within-absence in the early environment. PMID:25434884

  7. Study of the dissociation of molecular hydrogen

    NASA Technical Reports Server (NTRS)

    Vessot, R. F. C.

    1981-01-01

    Dissociators used to obtain an RF plasma discharge for hydrogen masers and the test system used for operation and evaluation of the dissociators are described. A compact sorption cartridge using a graphite matrix is tested as part of a hydrogen scavenging system. Testing of a vacuum enclosed hydrogen dissociator suitable for long term operation in space is described.

  8. Two-temperature models for nitrogen dissociation

    NASA Astrophysics Data System (ADS)

    da Silva, M. Lino; Guerra, V.; Loureiro, J.

    2007-12-01

    Accurate sets of nitrogen state-resolved dissociation rates have been reduced to two-temperature (translational T and vibrational Tv) dissociation rates. The analysis of such two-temperature dissociation rates shows evidence of two different dissociation behaviors. For Tv < 0.3 T dissociation proceeds predominantly from the lower-lying vibrational levels, whereas for Tv > 0.3 T dissociation proceeds predominantly form the near-dissociative vibrational levels, with an abrupt change of behavior at Tv = 0.3 T. These two-temperature sets have then been utilized as a benchmark for the comparison against popular multitemperature dissociation models (Park, Hansen, Marrone-Treanor, Hammerling, Losev-Shatalov, Gordiets, Kuznetsov, and Macheret-Fridman). This has allowed verifying the accuracy of each theoretical model, and additionally proposing adequate values for any semi-empirical parameters present in the different theories. The Macheret-Fridman model, who acknowledges the existence of the two aforementioned dissociation regimes, has been found to provide significantly more accurate results than the other models. Although these different theoretical approaches have been tested and validated solely for nitrogen dissociation processes, it is reasonable to expect that the general conclusions of this work, regarding the adequacy of the different dissociation models, could be extended to the description of arbitrary diatomic dissociation processes.

  9. Dissociative Functions in the Normal Mourning Process.

    ERIC Educational Resources Information Center

    Kauffman, Jeffrey

    1994-01-01

    Sees dissociative functions in mourning process as occurring in conjunction with integrative trends. Considers initial shock reaction in mourning as model of normal dissociation in mourning process. Dissociation is understood to be related to traumatic significance of death in human consciousness. Discerns four psychological categories of…

  10. Mechanical Dissociation of Retinal Neurons with Vibration

    NASA Astrophysics Data System (ADS)

    Motomura, Tamami; Hayashida, Yuki; Murayama, Nobuki

    The neuromorphic device, which implements the functions of biological neural circuits by means of VLSI technology, has been collecting much attention in the engineering fields in the last decade. Concurrently, progress in neuroscience research has revealed the nonlinear computation in single neuron levels, suggesting that individual neurons are not merely the circuit elements but computational units. Thus, elucidating the properties of neuronal signal processing is thought to be an essential step for developing the next generation of neuromorphic devices. In the present study, we developed a method for dissociating single neurons from specific sublayers of mammalian retinas with using no proteolytic enzymes but rather combining tissue incubation in a low-Ca2+ medium and the vibro-dissociation technique developed for the slices of brains and spinal cords previously. Our method took shorter time of the procedure, and required less elaborated skill, than the conventional enzymatic method did; nevertheless it yielded enough number of the cells available for acute electrophysiological experiments. The isolated retinal neurons were useful for measuring the nonlinear membrane conductances as well as the spike firing properties under the perforated-patch whole-cell configuration. These neurons also enabled us to examine the effects of proteolytic enzymes on the membrane excitability in those cells.

  11. Communication: Imaging wavefunctions in dissociative photoionization

    NASA Astrophysics Data System (ADS)

    Scott Hopkins, W.; Mackenzie, Stuart R.

    2011-08-01

    The dissociative ionization dynamics of excited electronic states of the xenon dimer, Xe2, have been studied using velocity map ion imaging (VMI). A one-colour, (2+1) resonant excitation scheme was employed to first excite and then ionize selected vibrational levels of the Xe2 6p 2[1/2]0 0_g^ + Rydberg state. Cationic fragments were then detected by the VMI. The data provide an outstanding example of the reflection principle in photodissociation with the full nodal structure of the Rydberg state wavefunctions clearly observed in the final Xe+ kinetic energy distributions without the need for scanning the excitation energy. Fitting of the observed distributions provides detailed and precise information on the form of the Xe2+ I(1/2g) potential energy curve involved which is in excellent agreement with the results of photoelectron imaging studies [Shubert and Pratt, J. Chem. Phys. 134, 044315 (2011), 10.1063/1.3533361]. Furthermore, the anisotropy of the product angular distributions yields information on the evolution of the electronic character of the ionic state with internuclear separation, R. The combination of the nature of dissociative ionization and the extent of the bound state wavefunctions provide information over an unusually wide range of internuclear separation R (ΔR > 0.75 Å). This would normally require scanning over a considerable energy region but is obtained in these studies at a fixed excitation energy.

  12. Does the tautomeric status of the adenine bases change upon the dissociation of the A*·A(syn) Topal-Fresco DNA mismatch? A combined QM and QTAIM atomistic insight.

    PubMed

    Brovarets', Ol'ha O; Zhurakivsky, Roman O; Hovorun, Dmytro M

    2014-02-28

    We have scrupulously explored the tautomerisation mechanism via the double proton transfer of the A*·A(syn) Topal-Fresco base mispair (C(s) symmetry), formed by the imino and amino tautomers of the adenine DNA base in the anti- and syn-conformations, respectively, bridging quantum-mechanical calculations with Bader's quantum theory of atoms in molecules. It was found that the A*·A(syn) ↔ A·A*(syn) tautomerisation is the asynchronous concerted process. It was established that the A*·A(syn) DNA mismatch is stabilized by the N6H···N6 (6.35) and N1H···N7 (6.17) hydrogen (H) bonds, whereas the A·A*(syn) base mispair (Cs) by the N6H···N6 (8.82) and N7H···N1 (9.78) H-bonds and the C8H···HC2 HH-bond (0.30 kcal mol(-1)). Using the sweeps of the energies of the intermolecular H-bonds, it was observed that the N6H···N6 and N1H···N7/N7H···N1 H-bonds are anti-cooperative and mutually weaken each other in the A*·A(syn) and A·A*(syn) mispairs. It was revealed that the A·A*(syn) DNA mismatch is a dynamically unstable structure with a short lifetime of 1.12 × 10(-13) s and any of its 6 low-frequency intermolecular vibrations can develop during this period of time. This observation makes it impossible to change the tautomeric status of the A bases upon the dissociation of the A*·A(syn) base mispair into the monomers during DNA replication.

  13. Does the tautomeric status of the adenine bases change upon the dissociation of the A*·A(syn) Topal-Fresco DNA mismatch? A combined QM and QTAIM atomistic insight.

    PubMed

    Brovarets', Ol'ha O; Zhurakivsky, Roman O; Hovorun, Dmytro M

    2014-02-28

    We have scrupulously explored the tautomerisation mechanism via the double proton transfer of the A*·A(syn) Topal-Fresco base mispair (C(s) symmetry), formed by the imino and amino tautomers of the adenine DNA base in the anti- and syn-conformations, respectively, bridging quantum-mechanical calculations with Bader's quantum theory of atoms in molecules. It was found that the A*·A(syn) ↔ A·A*(syn) tautomerisation is the asynchronous concerted process. It was established that the A*·A(syn) DNA mismatch is stabilized by the N6H···N6 (6.35) and N1H···N7 (6.17) hydrogen (H) bonds, whereas the A·A*(syn) base mispair (Cs) by the N6H···N6 (8.82) and N7H···N1 (9.78) H-bonds and the C8H···HC2 HH-bond (0.30 kcal mol(-1)). Using the sweeps of the energies of the intermolecular H-bonds, it was observed that the N6H···N6 and N1H···N7/N7H···N1 H-bonds are anti-cooperative and mutually weaken each other in the A*·A(syn) and A·A*(syn) mispairs. It was revealed that the A·A*(syn) DNA mismatch is a dynamically unstable structure with a short lifetime of 1.12 × 10(-13) s and any of its 6 low-frequency intermolecular vibrations can develop during this period of time. This observation makes it impossible to change the tautomeric status of the A bases upon the dissociation of the A*·A(syn) base mispair into the monomers during DNA replication. PMID:24418908

  14. Photoleucine Survives Backbone Cleavage by Electron Transfer Dissociation. A Near-UV Photodissociation and Infrared Multiphoton Dissociation Action Spectroscopy Study

    NASA Astrophysics Data System (ADS)

    Shaffer, Christopher J.; Martens, Jonathan; Marek, Aleš; Oomens, Jos; Tureček, František

    2016-07-01

    We report a combined experimental and computational study aimed at elucidating the structure of N-terminal fragment ions of the c type produced by electron transfer dissociation of photo-leucine (L*) peptide ions GL*GGKX. The c 4 ion from GL*GGK is found to retain an intact diazirine ring that undergoes selective photodissociation at 355 nm, followed by backbone cleavage. Infrared multiphoton dissociation action spectra point to the absence in the c 4 ion of a diazoalkane group that could be produced by thermal isomerization of vibrationally hot ions. The c 4 ion from ETD of GL*GGK is assigned an amide structure by a close match of the IRMPD action spectrum and calculated IR absorption. The energetics and kinetics of c 4 ion dissociations are discussed.

  15. [Dis-social personality disorder].

    PubMed

    Habermeyer, E; Herpertz, S C

    2006-05-01

    Deviant behavior is gaining in clinical importance if it is founded on stable, characteristic, and enduring patterns of psychopathologically relevant personality traits which have their onset in childhood or adolescence. The classification of these traits shows variations, so that a distinction between the ICD-10 diagnosis of dis-social personality disorder, DSM-IV diagnosis of antisocial personality disorder, and the concept "psychopathy" is necessary. Our knowledge about the biological basis of antisocial behavior includes neurophysiologic, psychophysiologic, and genetic findings. Also relevant are results of neurotransmitter studies and structural resp. functional neuroimaging findings. Psychosocial risk factors include parental deficits, rejection, disregard, unstable relations, and abuse. Efficient psychotherapeutic treatment is cognitive-behavioral. Pharmacologic treatment is largely "off-label". The diagnosis of antisocial and dis-social personality disorders allows no conclusions on criminal responsibility. In addition to psychiatric diagnostics, considerations on the severity of the disorder and its effects on the ability to inhibit actions are necessary.

  16. Paraphilia from a dissociative perspective.

    PubMed

    Ross, Colin A

    2008-12-01

    A dissociative structural model of the psyche can account for a wide range of symptoms across many DSM-IV categories, including sexual compulsions and addictions. The model leads to a distinct overall plan of treatment and a set of operationalized interventions aimed at integration of the self, rather than suppression of impulses. The model could be tested first in epidemiological studies and later in treatment outcome studies.

  17. Dissociative Photoionization of Diethyl Ether.

    PubMed

    Voronova, Krisztina; Mozaffari Easter, Chrissa M; Covert, Kyle J; Bodi, Andras; Hemberger, Patrick; Sztáray, Bálint

    2015-10-29

    The dissociative photoionization of internal energy selected diethyl ether ions was investigated by imaging photoelectron photoion coincidence spectroscopy. In a large, 5 eV energy range Et2O(+) cations decay by two parallel and three sequential dissociative photoionization channels, which can be modeled well using statistical theory. The 0 K appearance energies of the CH3CHOCH2CH3(+) (H-loss, m/z = 73) and CH3CH2O═CH2(+) (methyl-loss, m/z = 59) fragment ions were determined to be 10.419 ± 0.015 and 10.484 ± 0.008 eV, respectively. The reemergence of the hydrogen-loss ion above 11 eV is attributed to transition-state (TS) switching, in which the second, outer TS is rate-determining at high internal energies. At 11.81 ± 0.05 eV, a secondary fragment of the CH3CHOCH2CH3(+) (m/z = 73) ion, protonated acetaldehyde, CH3CH═OH(+) (m/z = 45) appears. On the basis of the known thermochemical onset of this fragment, a reverse barrier of 325 meV was found. Two more sequential dissociation reactions were examined, namely, ethylene and formaldehyde losses from the methyl-loss daughter ion. The 0 K appearance energies of 11.85 ± 0.07 and 12.20 ± 0.08 eV, respectively, indicate no reverse barrier in these processes. The statistical model of the dissociative photoionization can also be used to predict the fractional ion abundances in threshold photoionization at large temperatures, which could be of use in, for example, combustion diagnostics. PMID:26444101

  18. Dissociative symptoms and REM sleep.

    PubMed

    van Heugten-van der Kloet, Dalena; Merckelbach, Harald; Lynn, Steven Jay

    2013-12-01

    Llewellyn has written a fascinating article about rapid eye movement (REM) dreams and how they promote the elaborative encoding of recent memories. The main message of her article is that hyperassociative and fluid cognitive processes during REM dreaming facilitate consolidation. We consider one potential implication of this analysis: the possibility that excessive or out-of-phase REM sleep fuels dissociative symptomatology. Further research is warranted to explore the psychopathological ramifications of Llewellyn's theory. PMID:24304772

  19. [Differential diagnosis between dissociative disorders and schizophrenia].

    PubMed

    Shibayama, Masatoshi

    2011-01-01

    The differential diagnosis of dissociative disorders includes many psychiatric disorders, such as schizophrenia, bipolar disorders (especially bipolar II disorder), depressive disorder (especially atypical depression), epilepsy, Asperger syndrome, and borderline personality disorder. The theme of this paper is the differential diagnosis between dissociative disorders and schizophrenia. Schneiderian first-rank symptoms in schizophrenia are common in dissociative disorders, especially in dissociative identity disorder (DID). Many DID patients have been misdiagnosed as schizophrenics and treated with neuroleptics. We compared and examined Schneiderian symptoms of schizophrenia and those of dissociative disorders from a structural viewpoint. In dissociative disorders, delusional perception and somatic passivity are not seen. "Lateness" and "Precedence of the Other" originated from the concept of "Pattern Reversal" (H. Yasunaga)" is characteristic of schizophrenia. It is important to check these basic structure of schizophrenia in subjective experiences in differential diagnosis between dissociative disorders and schizophrenia.

  20. [Clinical Handling of Patients with Dissociative Disorders].

    PubMed

    Okano, Kenichiro

    2015-01-01

    This paper discusses the way informed psychiatrists are expected to handle dissociative patients in clinical situations, with a specific focus on dissociative identity disorders and dissociative fugue. On the initial interview with dissociative patients, information on their history of trauma and any nascent dissociative symptoms in their childhood should be carefully obtained. Their level of stress in their current life should also be assessed in order to understand their symptomatology, as well as to predict their future clinical course. A psychoeducational approach is crucial; it might be helpful to give information on dissociative disorder to these patients as well as their family members in order to promote their adherence to treatment. Regarding the symptomatology of dissociative disorders, detailed symptoms and the general clinical course are presented. It was stressed that dissociative identity disorder and dissociative fugue, the most high-profile dissociative disorders, are essentially different in their etiology and clinical presentation. Dissociative disorders are often confused with and misdiagnosed as psychotic disorders, such as schizophrenia. Other conditions considered in terms of the differential diagnosis include borderline personality disorder as well as temporal lobe epilepsy. Lastly, the therapeutic approach to dissociative identity disorder is discussed. Each dissociative identity should be understood as potentially representing some traumatically stressful event in the past. The therapist should be careful not to excessively promote the creation or elaboration of any dissociative identities. Three stages are proposed in the individual psychotherapeutic process. In the initial stage, a secure environment and stabilization of symptoms should be sought. The second stage consists of aiding the "host" personality to make use of other more adaptive coping skills in their life. The third stage involves coaching as well as continuous awareness of

  1. [Clinical Handling of Patients with Dissociative Disorders].

    PubMed

    Okano, Kenichiro

    2015-01-01

    This paper discusses the way informed psychiatrists are expected to handle dissociative patients in clinical situations, with a specific focus on dissociative identity disorders and dissociative fugue. On the initial interview with dissociative patients, information on their history of trauma and any nascent dissociative symptoms in their childhood should be carefully obtained. Their level of stress in their current life should also be assessed in order to understand their symptomatology, as well as to predict their future clinical course. A psychoeducational approach is crucial; it might be helpful to give information on dissociative disorder to these patients as well as their family members in order to promote their adherence to treatment. Regarding the symptomatology of dissociative disorders, detailed symptoms and the general clinical course are presented. It was stressed that dissociative identity disorder and dissociative fugue, the most high-profile dissociative disorders, are essentially different in their etiology and clinical presentation. Dissociative disorders are often confused with and misdiagnosed as psychotic disorders, such as schizophrenia. Other conditions considered in terms of the differential diagnosis include borderline personality disorder as well as temporal lobe epilepsy. Lastly, the therapeutic approach to dissociative identity disorder is discussed. Each dissociative identity should be understood as potentially representing some traumatically stressful event in the past. The therapist should be careful not to excessively promote the creation or elaboration of any dissociative identities. Three stages are proposed in the individual psychotherapeutic process. In the initial stage, a secure environment and stabilization of symptoms should be sought. The second stage consists of aiding the "host" personality to make use of other more adaptive coping skills in their life. The third stage involves coaching as well as continuous awareness of

  2. Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

    NASA Astrophysics Data System (ADS)

    Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

    2014-03-01

    Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

  3. Dissociative Tendencies and Facilitated Emotional Processing

    PubMed Central

    Oathes, Desmond J.; Ray, William J.

    2009-01-01

    Dissociation is a process linked to lapses of attention, history of abuse or trauma, compromised emotional memory, and a disintegrated sense of self. It is theorized that dissociation stems from avoiding emotional information, especially negative emotion, to protect a fragile psyche. The present study tested whether or not dissociaters do actually avoid processing emotion by asking groups scoring high or low on the Dissociative Experiences Scale to judge the affective valence of several types of emotional stimuli. Manipulations of valence, modality (pictures or words), task complexity, and personal relevance lead to results suggesting that dissociation is linked to facilitated rather than deficient emotional processing. Our results are consistent with a theory that sensitivity to emotional material may be a contributing factor in subsequent dissociation to avoid further elaboration of upsetting emotion in these individuals. The findings for dissociation further exemplify the influence of individual differences in the link between cognition and emotion. PMID:18837615

  4. Dissociating language and word meaning in the bilingual brain.

    PubMed

    Chee, Michael W L

    2006-12-01

    How do bilingual (or multilingual) persons keep different languages apart and switch between them as needs arise? Crinion et al. have used an ingenious method to dissociate brain regions sensitive to word meaning from those sensitive to the combination of meaning and language. This work should stimulate further research examining the role of subcortical areas in language processing and in context-appropriate language production.

  5. Dissociative identity disorder: Medicolegal challenges.

    PubMed

    Farrell, Helen M

    2011-01-01

    Persons with dissociative identity disorder (DID) often present in the criminal justice system rather than the mental health system and perplex experts in both professions. DID is a controversial diagnosis with important medicolegal implications. Defendants have claimed that they committed serious crimes, including rape or murder, while they were in a dissociated state. Asserting that their alter personality committed the bad act, defendants have pleaded not guilty by reason of insanity (NGRI). In such instances, forensic experts are asked to assess the defendant for DID and provide testimony in court. Debate continues over whether DID truly exists, whether expert testimony should be allowed into evidence, and whether it should exculpate defendants for their criminal acts. This article reviews historical and theoretical perspectives on DID, presents cases that illustrate the legal implications and controversies of raising an insanity defense based on multiple personalities, and examines the role of forensic experts asked to comment on DID with the goal of assisting clinicians in the medicolegal assessment of DID in relation to crimes.

  6. Dissociative recombination in planetary ionospheres

    NASA Technical Reports Server (NTRS)

    Fox, J. L.

    1993-01-01

    Ionization in planetary atmospheres can be produced by solar photoionization, photoelectron impact ionization, and, in auroral regions, by impact of precipitating particles. This ionization is lost mainly in dissociative recombination (DR) of molecular ions. Although atomic ions cannot undergo DR, they can be transformed locally through ion-molecule reactions into molecular ions, or they may be transported vertically or horizontally to regions of the atmosphere where such transformations are possible. Because DR reactions tend to be very exothermic, they can be an important source of kinetically or internally excited fragments. In interplanetary thermospheres, the neutral densities decrease exponentially with altitude. Below the homopause (or turbopause), the atmosphere is assumed to be throughly mixed by convection and/or turbulence. Above the homopause, diffusion is the major transport mechanism, and each species is distributed according to its mass, with the logarithmic derivative of the density with repect to altitude given approximately by -1/H, where H = kT/mg is the scale height. In this expression, T is the neutral temperature, g is the local acceleratiion of gravity, and m is the mass of the species. Thus lighter species become relatively more abundant, and heavier species less abundant, as the altitude increases. This variation of the neutral composition can lead to changes in the ion composition; furthermore, as the neutral densities decrease, dissociative recombination becomes more important relative to ion-neutral reactions as a loss mechanism for molecular ions.

  7. Mirror writing and a dissociative identity disorder.

    PubMed

    Le, Catherine; Smith, Joyce; Cohen, Lewis

    2009-01-01

    Individuals with dissociative identity disorder (DID) have been known to show varied skills and talents as they change from one dissociative state to another. For example, case reports have described people who have changed their handedness or have spoken foreign languages during their dissociative states. During an interview with a patient with DID, a surprising talent emerged when she wrote a sentence for the Folstein Mini-Mental State Exam-mirror writing. It is not known whether her mirror writing had a deeper level of meaning; however, it does emphasize the idiosyncratic nature of dissociative identity disorder.

  8. Dissociative Recombination without a Curve Crossing

    NASA Technical Reports Server (NTRS)

    Guberman, Steven L.

    1994-01-01

    Ab initio calculations show that a curve crossing is not always needed for a high dissociative- recombination cross section. For HeH(+), in which no neutral states cross the ion potential curve, dissociative recombination is driven by the nuclear kinetic-energy operator on adiabatic potential curves. The kinetic-energy derivative operator allows for capture into repulsive curves that are outside of the classical turning points for the nuclear motion. The dominant dissociative route is the C (2)Sigma(+) state leading to H(n = 2) atoms. An analogous mechanism is proposed for the dissociative recombination of H3(+).

  9. Investigation of intense femto-second laser ionization and dissociation of methane with time-dependent density-functional approach

    NASA Astrophysics Data System (ADS)

    Irani, E.; Sadighi-Bonabi, R.; Anvari, A.

    2014-06-01

    Three dimensional calculations of electronic dynamics of CH4 in a strong laser field are presented with time-dependent density-functional theory. Time evolution of dipole moment and electron localization function is presented. The dependence of dissociation rate on the laser characters is shown and optimal effective parameters are evaluated. The optimum field leads to 76% dissociation probability for GAUSSIAN envelope and 40 fs (FWHM) at 1016 W cm-2. The dissociation probability is calculated by optimum convolution of dual short pulses. By combining of field assisted dissociation process and Ehrenfest molecular dynamics, time variation of bond length, velocity and orientation effect are investigated.

  10. Dissociative symptoms and dissociative disorder comorbidity in patients with obsessive-compulsive disorder.

    PubMed

    Belli, Hasan; Ural, Cenk; Vardar, Melek Kanarya; Yesılyurt, Sema; Oncu, Fatıh

    2012-10-01

    The present study attempted to assess the dissociative symptoms and overall dissociative disorder comorbidity in patients with obsessive-compulsive disorder (OCD). In addition, we examined the relationship between the severity of obsessive-compulsive symptoms and dissociative symptoms. All patients admitted for the first time to the psychiatric outpatient unit were included in the study. Seventy-eight patients had been diagnosed as having OCD during the 2-year study period. Patients had to meet the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition criteria for OCD. Most (76.9%; n = 60) of the patients were female, and 23.1% (n = 18) of the patients were male. Dissociation Questionnaire was used to measure dissociative symptoms. The Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition Dissociative Disorders interviews and Yale-Brown Obsessive Compulsive Checklist and Severity Scale were used. Eleven (14%) of the patients with OCD had comorbid dissociative disorder. The most prevalent disorder in our study was dissociative depersonalization disorder. Dissociative amnesia and dissociative identity disorder were common as well. The mean Yale-Brown score was 23.37 ± 7.27 points. Dissociation Questionnaire scores were between 0.40 and 3.87 points, and the mean was 2.23 ± 0.76 points. There was a statistically significant positive correlation between Yale-Brown points and Dissociation Questionnaire points. We conclude that dissociative symptoms among patients with OCD should alert clinicians for the presence of a chronic and complex dissociative disorder. Clinicians may overlook an underlying dissociative process in patients who have severe symptoms of OCD. However, a lack of adequate response to cognitive-behavioral and drug therapy may be a consequence of dissociative process.

  11. The multidimensional inventory of dissociation (MID): A comprehensive measure of pathological dissociation.

    PubMed

    Dell, Paul F

    2006-01-01

    This article describes the development and validation of the Multidimensional Inventory of Dissociation (MID). The MID is a 218-item, self-administered, multiscale instrument that comprehensively assesses the phenomenological domain of pathological dissociation and diagnoses the dissociative disorders. The MID measures 14 major facets of pathological dissociation; it has 23 dissociation diagnostic scales that simultaneously operationalize (1) the subjective/ phenomenological domain of pathological dissociation and (2) the hypothesized dissociative symptoms of dissociative identity disorder (Dell, 2001a). The MID was designed for clinical research and for diagnostic assessment of patients who present with a mixture of dissociative, posttraumatic, and borderline symptoms. The MID demonstrated internal reliability, temporal stability, convergent validity, discriminant validity, and construct validity. The MID also exhibited incremental validity over the Dissociative Experiences Scale (DES) by predicting an additional 18% of the variance in weighted abuse scores on the Traumatic Experiences Questionnaire (TEQ). Confirmatory factor analysis (CFA) did not support a one-factor model of the MID's clinical scales (i.e., the 14 facets and the 23 diagnostic symptoms). In contrast, however, CFA of the MID's factor scales (Dell & Lawson, 2005) has strongly supported a one-factor model. It was concluded that both the MID's 168 dissociation items and the construct of pathological dissociation have a second-order, unifactorial structure.

  12. The differential diagnosis of epilepsy, pseudoseizures, dissociative identity disorder, and dissociative disorder not otherwise specified.

    PubMed

    Bowman, E S; Coons, P M

    2000-01-01

    The authors review the co-occurrences of dissociative symptoms and disorders with epilepsy and pseudo-seizures and examine newer diagnostic instruments that assist in accurate diagnosis of persons with concomitant seizure behaviors and dissociative symptoms. They also review seizure behaviors and electroencephalographic findings in persons with dissociative identity disorder (DID) and dissociative disorder not otherwise specified (DDNOS) and dissociative symptoms in persons with epilepsy and with pseudoseizures. Dissociative symptoms in 15 patients with epilepsy and 15 with pseudo-seizures were examined using the Dissociative Experiences Scale (DES) and the Structured Clinical Interview for DSM-IV Dissociative Disorders (SCID-D). On the SCID-D, pseudo-seizure patients had significantly higher dissociative symptom scores than epileptic patients, but DES scores did not reliably distinguish epileptic and pseudo-seizure patients. Misdiagnosis of persons with seizures and dissociative symptoms can be avoided by careful adherence to DSM dissociative disorder criteria, the use of video-EEG monitoring, and systematic assessment of dissociative symptoms with the SCID-D.

  13. Molecular dissociation in dilute gas

    SciTech Connect

    Renfrow, S.N.; Duggan, J.L.; McDaniel, F.D. |

    1999-06-01

    The charge state distributions (CSD) produced during molecular dissociation are important to both Trace Element Accelerator Mass Spectrometry (TEAMS) and the ion implantation industry. The CSD of 1.3{endash}1.7 MeV SiN{sup +}, SiMg{sup +}, SiMn{sup +}, and SiZn{sup +} molecules have been measured for elements that do not form atomic negative ions (N, Mg, Mn, and Zn) using a NEC Tandem Pelletron accelerator. The molecules were produced in a Cs sputter negative ion source, accelerated, magnetically analyzed, and then passed through an N{sub 2} gas cell. The neutral and charged breakups where analyzed using an electrostatic deflector and measured with particle detectors. Equilibrium CSD were determined and comparisons made between molecular and atomic ion data. {copyright} {ital 1999 American Institute of Physics.}

  14. The Dissociative Recombination of OH(+)

    NASA Technical Reports Server (NTRS)

    Guberman, Steven L.

    1995-01-01

    Theoretical quantum chemical calculations of the cross sections and rates for the dissociative recombination of the upsilon = 0 level of the ground state of OH(+) show that recombination occurs primarily along the 2 (2)Pi diabatic route. The products are 0((1)D) and a hot H atom with 6.1 eV kinetic energy. The coupling to the resonances is very small and the indirect recombination mechanism plays only a minor role. The recommended value for the rate coefficient is (6.3 +/- 0.7) x 10(exp -9)x (T(e)/1300)(exp -0.48) cu.cm/s for 10 less than T(e) less than 1000 K.

  15. Dissociative depression among women in the community.

    PubMed

    Sar, Vedat; Akyüz, Gamze; Oztürk, Erdinç; Alioğlu, Firdevs

    2013-01-01

    This study screened the prevalence and correlates of dissociative disorders among depressive women in the general population. The Dissociative Disorders Interview Schedule and the posttraumatic stress disorder (PTSD) and borderline personality disorder sections of the Structured Clinical Interview for DSM-IV were administered to 628 women in 500 homes. The prevalence of current major depressive episode was 10.0%. Of the women, 26 (40.6%) had the lifetime diagnosis of a DSM-IV, dissociative disorder, yielding a prevalence of 4.1% for dissociative depression. This group was younger (mean age = 30.7 years) than the nondissociative depression women (mean age = 39.6 years). There was no difference between the 2 groups on comorbid somatization disorder, PTSD, or borderline personality disorder. Besides suicide attempts, the dissociative group was characterized by secondary features of dissociative identity disorder; Schneiderian symptoms; borderline personality disorder criteria; and extrasensory perceptions, including possession experiences. They reported suicidality, thoughts of guilt and worthlessness, diminished concentration and indecisiveness, and appetite and weight changes more frequently than the nondissociative group. Early cessation of school education and childhood sexual abuse were frequently reported by the dissociative depression group. With its distinct features, the concept of dissociative depression may facilitate understanding of treatment resistance in, development of better psychotherapy strategies for, and new thinking on the neurobiology and pharmacotherapy of depressive disorders. PMID:23796173

  16. Dissociation and the Development of Psychopathology.

    ERIC Educational Resources Information Center

    Putnam, Frank W.; Trickett, Penelope K.

    This paper reviews the research on dissociation and the development of psychopathology in children and adolescents. Definitions and dimensions of dissociation are addressed, noting its range from normative daydreaming to the extremes found in individuals with multiple personality disorder. Memory dysfunctions, disturbances of identity, passive…

  17. Dissociative depression among women in the community.

    PubMed

    Sar, Vedat; Akyüz, Gamze; Oztürk, Erdinç; Alioğlu, Firdevs

    2013-01-01

    This study screened the prevalence and correlates of dissociative disorders among depressive women in the general population. The Dissociative Disorders Interview Schedule and the posttraumatic stress disorder (PTSD) and borderline personality disorder sections of the Structured Clinical Interview for DSM-IV were administered to 628 women in 500 homes. The prevalence of current major depressive episode was 10.0%. Of the women, 26 (40.6%) had the lifetime diagnosis of a DSM-IV, dissociative disorder, yielding a prevalence of 4.1% for dissociative depression. This group was younger (mean age = 30.7 years) than the nondissociative depression women (mean age = 39.6 years). There was no difference between the 2 groups on comorbid somatization disorder, PTSD, or borderline personality disorder. Besides suicide attempts, the dissociative group was characterized by secondary features of dissociative identity disorder; Schneiderian symptoms; borderline personality disorder criteria; and extrasensory perceptions, including possession experiences. They reported suicidality, thoughts of guilt and worthlessness, diminished concentration and indecisiveness, and appetite and weight changes more frequently than the nondissociative group. Early cessation of school education and childhood sexual abuse were frequently reported by the dissociative depression group. With its distinct features, the concept of dissociative depression may facilitate understanding of treatment resistance in, development of better psychotherapy strategies for, and new thinking on the neurobiology and pharmacotherapy of depressive disorders.

  18. Childhood Stuttering and Dissociations across Linguistic Domains

    ERIC Educational Resources Information Center

    Anderson, Julie D.; Pellowski, Mark W.; Conture, Edward G.

    2005-01-01

    The purpose of this investigation was to evaluate the possible presence of dissociations in the speech and language skills of young children who do (CWS) and do not stutter (CWNS) using a correlation-based statistical procedure [Bates, E., Appelbaum, M., Salcedo, J., Saygin, A. P., & Pizzamiglio, L. (2003). Quantifying dissociations in…

  19. [Dissociative disorder and self-injury].

    PubMed

    Noma, Shun'ichi

    2011-01-01

    Both the number of patients with dissociative disorder and that of those with self-injury have been increasing since the end of the twentieth century, suggesting that dissociation and self-injury might be closely related. When dissociative disorder coexists with self-injury, it implies self-punishment and a wish to be understood by others. Although many cases of self-injury observed since 2000 lacked traumatic experiences and were not accompanied by pathological dissociative symptoms, the patients did have dissociative tendencies. According to the results of our study examining self-injury in patients with eating disorders, we observed that self-injury, dissociative tendency and insulation from others are related to each other. This suggests that affects, sensations and representations are dissociated, losing their normal response order, and that the pervasive idea that "pain=secure" is formed in a patient from childhood based on influence from their parents. Self-injury appears to be an activation of this pervasive idea that is triggered by a stressful situation, when the dissociative psychological segmentation of effects and their representations are present in the background.

  20. A Hierarchical Process-Dissociation Model

    ERIC Educational Resources Information Center

    Rouder, Jeffrey N.; Lu, Jun; Morey, Richard D.; Sun, Dongchu; Speckman, Paul L.

    2008-01-01

    In fitting the process-dissociation model (L. L. Jacoby, 1991) to observed data, researchers aggregate outcomes across participant, items, or both. T. Curran and D. L. Hintzman (1995) demonstrated how biases from aggregation may lead to artifactual support for the model. The authors develop a hierarchical process-dissociation model that does not…

  1. The expectancy of threat and peritraumatic dissociation

    PubMed Central

    McDonald, Pamela; Bryant, Richard A.; Silove, Derrick; Creamer, Mark; O'Donnell, Meaghan; McFarlane, Alexander C.

    2013-01-01

    Background Peritraumatic dissociation is one of the most critical acute responses to a traumatic experience, partly because it predicts subsequent posttraumatic stress disorder. Despite this, there is little understanding about the factors that influence peritraumatic dissociation. This study investigated the extent to which peritraumatic dissociation is predicted by the amount of perceived warning that participants had of the impact of the trauma. Method Randomized eligible admissions to four major trauma hospitals (N=243) were assessed during hospital admission with the Peritraumatic Dissociation Experiences Questionnaire (PDEQ) and the perceived warning that participants had before the trauma impact occurred. Results Whereas female gender predicted both Awareness and Derealization subscale scores on the PDEQ, perceived warning also predicted scores on the Derealization subscale. Conclusions This finding suggests that the degree of anticipated threat may contribute to peritraumatic dissociation. PMID:24363835

  2. The Shutdown Dissociation Scale (Shut-D)

    PubMed Central

    Schalinski, Inga; Schauer, Maggie; Elbert, Thomas

    2015-01-01

    The evolutionary model of the defense cascade by Schauer and Elbert (2010) provides a theoretical frame for a short interview to assess problems underlying and leading to the dissociative subtype of posttraumatic stress disorder. Based on known characteristics of the defense stages “fright,” “flag,” and “faint,” we designed a structured interview to assess the vulnerability for the respective types of dissociation. Most of the scales that assess dissociative phenomena are designed as self-report questionnaires. Their items are usually selected based on more heuristic considerations rather than a theoretical model and thus include anything from minor dissociative experiences to major pathological dissociation. The shutdown dissociation scale (Shut-D) was applied in several studies in patients with a history of multiple traumatic events and different disorders that have been shown previously to be prone to symptoms of dissociation. The goal of the present investigation was to obtain psychometric characteristics of the Shut-D (including factor structure, internal consistency, retest reliability, predictive, convergent and criterion-related concurrent validity). A total population of 225 patients and 68 healthy controls were accessed. Shut-D appears to have sufficient internal reliability, excellent retest reliability, high convergent validity, and satisfactory predictive validity, while the summed score of the scale reliably separates patients with exposure to trauma (in different diagnostic groups) from healthy controls. The Shut-D is a brief structured interview for assessing the vulnerability to dissociate as a consequence of exposure to traumatic stressors. The scale demonstrates high-quality psychometric properties and may be useful for researchers and clinicians in assessing shutdown dissociation as well as in predicting the risk of dissociative responding. PMID:25976478

  3. Dissociation and Memory Fragmentation in Posttraumatic Stress Disorder: An Evaluation of the Dissociative Encoding Hypothesis

    PubMed Central

    Bedard-Gilligan, Michele; Zoellner, Lori A.

    2012-01-01

    Several prominent theories of posttraumatic stress disorder (PTSD) posit that peritraumatic dissociation results in insufficient encoding of the trauma memory and that persistent dissociation prevents memory elaboration, resulting in memory fragmentation and PTSD. In this review, we summarize the empirical literature on peritraumatic and trait dissociation and trauma narrative fragmentation as measured by meta-memory and rater/objective coding. Across 16 studies to date, the association between dissociation and fragmentation was most prominent when examining peritraumatic dissociation and patient's own ratings of memory fragmentation. This relationship did not hold when examining trait dissociation or rater-coded or computer-generated measures of fragmentation. Thus, initial evidence points more toward a strong self-reported association between constructs that is not supported on more objective fragmentation coding. Measurement overlap, construct ambiguity, and exclusion of potential confounds may underlie lack of a strong association between dissociation and objective-rated fragmentation. PMID:22348400

  4. Shielding of CO from dissociating radiation in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Glassgold, A. E.; Huggins, P. J.; Langer, W. D.

    1985-01-01

    The paper investigates the photodissociation of CO in interstellar clouds in the light of recent laboratory studies which suggest that line rather than continuum processes dominate its dissociation by ultraviolet radiation. Using a simple radiative transfer model, the shielding of representative dissociating bands is estimated, including self-shielding, mutual shielding between different isotopes, and near coincidences with strong lines of H2. Each of these processes materially affects the photodestruction rates of the various isotopic species in the transition regions of molecular clouds. These results are combined with an appropriate gas phase chemical model to determine how the abundances of the CO isotopes vary with depth into the cloud. It is found that self-shielding and mutual shielding cause significant variations in isotopic ratios. In addition, fractionation enhances species containing C-13. The relationship between the column densities of CO and H2 is found to vary for the different isotopes and to be sensitive to local conditions.

  5. Dissociation dynamics in the dissociative electron attachment to carbon dioxide

    NASA Astrophysics Data System (ADS)

    Nag, Pamir; Nandi, Dhananjay

    2015-05-01

    Dissociative electron attachment (DEA) to gas phase CO2 has been probed using a velocity slice imaging technique. DEA to CO2 produces only an O- ionic fragment and shows two major resonances located at 4.4 and 8.2 eV, respectively. The kinetic energy and angular distribution of the O- ions are measured around the second resonance with higher efficiency and sensitivity that provide details of the DEA dynamics. The kinetic energy distributions are in good agreement with the previous reports. However, the distinct angular distributions show substantial difference from the two recent studies within the limited electron energies. Our angular distribution results show two negative ion resonant states are involved in the underlying DEA process at the entire electron energies over the second resonance. We discussed the recent conflicting findings in the angular distribution results. The forward-backward asymmetry observed in the angular distributions is explained due to the interference effect of different partial waves associated with the attaching electron.

  6. From state dissociation to status dissociatus.

    PubMed

    Antelmi, Elena; Ferri, Raffaele; Iranzo, Alex; Arnulf, Isabelle; Dauvilliers, Yves; Bhatia, Kailash P; Liguori, Rocco; Schenck, Carlos H; Plazzi, Giuseppe

    2016-08-01

    The states of being are conventionally defined by the simultaneous occurrence of behavioral, neurophysiological and autonomic descriptors. State dissociation disorders are due to the intrusion of features typical of a different state into an ongoing state. Disorders related to these conditions are classified according to the ongoing main state and comprise: 1) Dissociation from prevailing wakefulness as seen in hypnagogic or hypnopompic hallucinations, automatic behaviors, sleep drunkenness, cataplexy and sleep paralysis 2) Dissociation from rapid eye movement (REM) sleep as seen in REM sleep behavior disorder and lucid dreaming and 3) Dissociation from NREM sleep as seen in the disorders of arousal. The extreme expression of states dissociation is characterized by the asynchronous occurrence of the various components of the different states that prevents the recognition of any state of being. This condition has been named status dissociatus. According to the underlying disorders/diseases and to their severity, among status dissociatus we may recognize disorders in which such an extreme dissociation occurs only at night time or intermittently (i.e., autoimmune encephalopathies, narcolepsy type 1 and IgLON5 parasomnia), and others in which it occurs nearly continuously with complete loss of any conventionally defined state of being, and of the circadian pattern (agrypnia excitata). Here, we render a comprehensive review of all diseases/disorders associated with state dissociation and status dissociatus and propose a critical classification of this complex scenario. PMID:26431902

  7. From state dissociation to status dissociatus.

    PubMed

    Antelmi, Elena; Ferri, Raffaele; Iranzo, Alex; Arnulf, Isabelle; Dauvilliers, Yves; Bhatia, Kailash P; Liguori, Rocco; Schenck, Carlos H; Plazzi, Giuseppe

    2016-08-01

    The states of being are conventionally defined by the simultaneous occurrence of behavioral, neurophysiological and autonomic descriptors. State dissociation disorders are due to the intrusion of features typical of a different state into an ongoing state. Disorders related to these conditions are classified according to the ongoing main state and comprise: 1) Dissociation from prevailing wakefulness as seen in hypnagogic or hypnopompic hallucinations, automatic behaviors, sleep drunkenness, cataplexy and sleep paralysis 2) Dissociation from rapid eye movement (REM) sleep as seen in REM sleep behavior disorder and lucid dreaming and 3) Dissociation from NREM sleep as seen in the disorders of arousal. The extreme expression of states dissociation is characterized by the asynchronous occurrence of the various components of the different states that prevents the recognition of any state of being. This condition has been named status dissociatus. According to the underlying disorders/diseases and to their severity, among status dissociatus we may recognize disorders in which such an extreme dissociation occurs only at night time or intermittently (i.e., autoimmune encephalopathies, narcolepsy type 1 and IgLON5 parasomnia), and others in which it occurs nearly continuously with complete loss of any conventionally defined state of being, and of the circadian pattern (agrypnia excitata). Here, we render a comprehensive review of all diseases/disorders associated with state dissociation and status dissociatus and propose a critical classification of this complex scenario.

  8. State dissociation, human behavior, and consciousness.

    PubMed

    Mahowald, Mark W; Cramer Bornemann, Michel A; Schenck, Carlos H

    2011-01-01

    Sleep is clearly not only a whole-brain or global phenomenon, but can also be a local phenomenon. This accounts for the fact that the primary states of being (wakefulness, NREM sleep, and REM sleep) are not necessarily mutually exclusive, and components of these states may appear in various combinations, with fascinating clinical consequences. Examples include: sleep inertia, narcolepsy, sleep paralysis, lucid dreaming, REM sleep behavior disorder, sleepwalking, sleep terrors, out-of-body experiences, and reports of alien abduction. The incomplete declaration of state likewise has implications for consciousness - which also has fluid boundaries. Fluctuations in the degree of consciousness are likely explained by abnormalities of a "spatial and temporal binding rhythm" which normally results in a unified conscious experience. Dysfunctional binding may play a role in anesthetic states, autism, schizophrenia, and neurodegenerative disorders. Further study of the broad spectrum of dissociated states of sleep and wakefulness that are closely linked with states of consciousness and unconsciousness by basic neuroscientists, clinicians, and members of the legal profession will provide scientific, clinical and therapeutic insights, with forensic implications. PMID:21906025

  9. State dissociation, human behavior, and consciousness.

    PubMed

    Mahowald, Mark W; Cramer Bornemann, Michel A; Schenck, Carlos H

    2011-01-01

    Sleep is clearly not only a whole-brain or global phenomenon, but can also be a local phenomenon. This accounts for the fact that the primary states of being (wakefulness, NREM sleep, and REM sleep) are not necessarily mutually exclusive, and components of these states may appear in various combinations, with fascinating clinical consequences. Examples include: sleep inertia, narcolepsy, sleep paralysis, lucid dreaming, REM sleep behavior disorder, sleepwalking, sleep terrors, out-of-body experiences, and reports of alien abduction. The incomplete declaration of state likewise has implications for consciousness - which also has fluid boundaries. Fluctuations in the degree of consciousness are likely explained by abnormalities of a "spatial and temporal binding rhythm" which normally results in a unified conscious experience. Dysfunctional binding may play a role in anesthetic states, autism, schizophrenia, and neurodegenerative disorders. Further study of the broad spectrum of dissociated states of sleep and wakefulness that are closely linked with states of consciousness and unconsciousness by basic neuroscientists, clinicians, and members of the legal profession will provide scientific, clinical and therapeutic insights, with forensic implications.

  10. Formulation and numerical analysis of diatomic molecular dissociation using Boltzmann kinetic equation

    NASA Astrophysics Data System (ADS)

    Yano, Ryosuke; Suzuki, Kojiro; Kuroda, Hisayasu

    2007-01-01

    The direct description of chemical reactions by the Boltzmann equation still involves some difficulties in the kinetic theory. In this paper, we describe diatomic molecular dissociation due to transitions of vibrational quantum states resulting from inelastic collisions. These can be described by the Wang Chang-Uhlenbeck (WCU) equation. To avoid direct evaluation of the strong nonlinear collision kernel of the WCU equation, we used a kinetic equation. For accurate description of the dissociation process, we describe improvements we made to the conventional inelastic collision model (the so-called Morse model). Combining this inelastic collision model with the gas mixture model by Oguchi, we formulated a model for representing diatomic molecular dissociations. We validated this model by simulating a hypersonic shock layer with diatomic molecular dissociation.

  11. Alexithymia and its relationships with dissociative experiences and Internet addiction in a nonclinical sample.

    PubMed

    De Berardis, Domenico; D'Albenzio, Alessandro; Gambi, Francesco; Sepede, Gianna; Valchera, Alessandro; Conti, Chiara M; Fulcheri, Mario; Cavuto, Marilde; Ortolani, Carla; Salerno, Rosa Maria; Serroni, Nicola; Ferro, Filippo Maria

    2009-02-01

    The aim of the present study was to evaluate alexithymia, dissociative experiences, and Internet addiction (IA) in a nonclinical sample of 312 undergraduate students, identifying predictive factors associated with the possible risk of developing IA. We found that alexithymics had more consistent dissociative experiences, lower self-esteem, and higher obsessive-compulsive symptoms than nonalexithymics. In addition, alexithymics reported a higher potential risk for IA when compared to nonalexithymics. Difficulty in identifying feelings, higher dissociative experiences, lower self-esteem, and higher impulse dysregulation were associated with higher IA. Thus, a combination of alexithymia, dissociative experiences, low self-esteem, and impulse dysregulation may be a risk factor for IA, at least in a nonclinical sample.

  12. A new concept Tandem thermal dissociator/electron impact ion source for RIB generation

    SciTech Connect

    Alton, G.D.; Williams, C.

    1995-12-31

    An innovative thermal dissociation/electron impact ionization positive ion source is presently under design at the Oak Ridge National Laboratory for potential use for generating RIBs at the Holifield Radioactive Ion Beam Facility (HRIBF). Because of the low probability of simultaneously dissociating and efficiently ionizing the individual atomic constituents with conventional, hot-cathode, electron-impact ion sources, the ion beams extracted from these sources often appear as a mixture of several molecular sideband beams. In this way, the intensity of the species of interest is diluted. We have conceived an Ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high efficiency characteristics of an electron impact ionization source. If the concept proves to be a viable option, the source will be used as a complement to the electron beam plasma ion sources already in use at the HRIBF. The design features and principles of operation of the source are described in this article.

  13. Momentum Imaging of the Dynamics of Dissociative Electron Attachment to Uracil

    NASA Astrophysics Data System (ADS)

    Slaughter, Dan; Kawarai, Yu; Weber, Thorsten; Azuma, Yoshiro; Winstead, Carl; McKoy, Vince; Belkacem, Ali

    2013-05-01

    Observation of the dynamics of dissociative electron attachment (DEA) in biomolecules has recently become possible by momentum imaging of the fragments resulting from the dissociating transient anion resonance. A momentum spectrometer featuring a 4 π solid angle of detection is combined with a pulsed electron beam and effusive molecular beam in a crossed geometry to measure the full 3D momentum distribution of dissociating negative ions. Guided by electronic structure calculations that indicate the most likely orientation of the molecule at the time of attachment, we present key aspects of the dynamics of ring-breaking dissociation of the transient anion formed upon DEA to the nucleobase uracil. Performed under the auspices of the US DOE by LBNL under Contract DE-AC02-05CH11231.

  14. [Posttraumatic stress disorder, dissociation and self-destructive behavior in borderline patients

    PubMed

    Spitzer, Carsten; Effler, Kerstin; Freyberger, Harald J.

    2000-01-01

    We studied traumatic childhood experiences, comorbid posttraumatic stress disorders (PTSD), dissociation and self-destructive behavior in 30 inpatients with a borderline personality disorder. A standardized interview for the assessment of PTSD, the Dissociative Experience Scale and the Symptom-checklist were administered. Results were compared to a control of inpatients with neurotic disorders matched for gender and age. Borderline patients showed significantly more childhood sexual and physical abuse as well as emotional neglect than the control patients. Of the borderline patients, 67% met criteria for PTSD and only 13% of the control group. Dissociative symptoms were significantly more frequent in borderline patients and predicted in combination with PTSD symptoms and self-destructive behavior. We discuss our findings with respect to their etiological and clinical significance and propose a model for self-destruction in borderline patients which focusses on dissociation and trauma.

  15. Dissociative identity disorder: a controversial diagnosis.

    PubMed

    Gillig, Paulette Marie

    2009-03-01

    A brief description of the controversies surrounding the diagnosis of dissociative identity disorder is presented, followed by a discussion of the proposed similarities and differences between dissociative identity disorder and borderline personality disorder. The phenomenon of autohypnosis in the context of early childhood sexual trauma and disordered attachment is discussed, as is the meaning of alters or alternate personalities. The author describes recent neurosciences research that may relate the symptoms of dissociative identity disorder to demonstrable disordered attention and memory processes. A clinical description of a typical patient presentation is included, plus some recommendations for approaches to treatment.

  16. Wavepacket theory of collisional dissociation in molecules

    SciTech Connect

    Kulander, K.

    1980-01-01

    An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H/sub 2/ system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process.

  17. Dissociative Ionization of Pyridine by Electron Impact

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher; Huo, Winifred; Kwak, Dochan (Technical Monitor)

    2002-01-01

    In order to understand the damage of biomolecules by electrons, a process important in radiation damage, we undertake a study of the dissociative ionization (DI) of pyridine (C5H5N) from the low-lying ionization channels. The methodology used is the same as in the benzene study. While no experimental DI data are available, we compare the dissociation products from our calculations with the dissociative photoionization measurements of Tixier et al. using dipole (e, e(+) ion) coincidence spectroscopy. Comparisons with the DI of benzene is also made so as to understand the difference in DI between a heterocyclic and an aromatic molecule.

  18. Theory of dissociative tunneling ionization

    NASA Astrophysics Data System (ADS)

    Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

    2016-05-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees of freedom. In the regime where the BO approximation is applicable, imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally, the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fields, where the BO approximation does not apply, the weak-field asymptotic theory describes the spectrum accurately.

  19. Dissociative recombination of CH4(+).

    PubMed

    Thomas, Richard D; Kashperka, Iryna; Vigren, E; Geppert, Wolf D; Hamberg, Mathias; Larsson, Mats; af Ugglas, Magnus; Zhaunerchyk, Vitali

    2013-10-01

    CH4(+) is an important molecular ion in the astrochemistry of diffuse clouds, dense clouds, cometary comae, and planetary ionospheres. However, the rate of one of the common destruction mechanisms for molecular ions in these regions, dissociative recombination (DR), is somewhat uncertain. Here, we present absolute measurements for the DR of CH4(+) made using the heavy ion storage ring CRYRING in Stockholm, Sweden. From our collision-energy dependent cross-sections, we infer a thermal rate constant of k(Te) = 1.71(±0.02) × 10(–6)(Te/300)(−0.66(±0.02)) cm3 s(–1) over the region of electron temperatures 10 ≤ Te ≤ 1000 K. At low collision energies, we have measured the branching fractions of the DR products to be CH4 (0.00 ± 0.00); CH3 + H (0.18 ± 0.03); CH2 + 2H (0.51 ± 0.03); CH2 + H2 (0.06 ± 0.01); CH + H2 + H (0.23 ± 0.01); and CH + 2H2 (0.02 ± 0.01), indicating that two or more C–H bonds are broken in 80% of all collisions.

  20. [Significance of and considerations relating to the diagnosis of dissociation].

    PubMed

    Koreki, Akihiro

    2011-01-01

    Dissociation involves a variety of clinical concepts, and some disorders are also similar to but not the same as dissociation. Dissociative disorder is considered to be a pathological phenomenon based on a psychological mechanism. Accurate diagnosis is very important to ensure that patients receive adequate treatment, although such consideration is not unique to dissociative disorder. Accordingly, there is a need to carefully distinguish dissociation from other disorders. In this article, we outline a number of dissociative and dissociative-like states from the symptoms of amnesia, depersonalization and switching. In particular, we highlight the differences between transient global amnesia and dissociative amnesia, and imaginary companions and dissociative alter personality. Additionally, as the symptoms of conditions such as dissociative amnesia and dissociative identity disorder are easily confused, we also made efforts to organize them.

  1. Collision-induced gas phase dissociation rates

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1990-01-01

    The Landau-Zener theory of reactive cross sections was applied to diatomic molecules dissociating from a ladder of vibrational states. The result predicts a dissociation rate that is quite well duplicated by an Arrhenius function having a preexponential temperature dependence of about T(sub -1/2), at least for inert collision partners. This relation fits experimental data reasonably well. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators, the results are about the same as given by Hammerling, Kivel, and Teare in their analytic approximation for harmonic oscillators, though at very high temperature a correction for the partition function limit is included. The empirical correction for vibration nonequilibrium proposed by Park, which is a convenient algorithm for CFD calculations, is modified to prevent a drastic underestimation of dissociation rates that occurs with this method when vibrational temperature is much smaller than the kinetic temperature of the gas.

  2. Research Reports: Hallucinogens and Dissociative Drugs

    MedlinePlus

    ... in bizarre or dangerous behavior. Hallucinogens such as LSD, psilocybin, peyote, DMT, and ayahuasca cause emotions to ... Take Hallucinogenic or Dissociative Drugs? How Do Hallucinogens (LSD, Psilocybin, Peyote, DMT, and Ayahuasca) Affect the Brain ...

  3. Dissociative identity disorder presenting as dermatitis artefacta.

    PubMed

    Ozmen, Mine; Erdogan, Ayten; Aydemir, Ertugrul H; Oguz, Oya

    2006-06-01

    Dermatitis artefacta is a rare psychiatric condition characterized by rubbing of skin blisters and denial of self-infliction. Dissociation may be comorbid with self-injurious behavior. A background of emotional disturbances during formative years and in later life often results in feelings of isolation and insecurity, which can lead to dissociation as a primary defense mechanism used to overcome traumatic events. In this case report, we describe a female patient with dermatitis artefacta associated with dissociative identity disorder. The patient was a 14-year-old girl. Multiple large, deep ulcerations with unnatural shapes were seen on her left forearm. The ulcerations were thought to be self-inflicted. Psychiatric examination revealed that she had a different identity, and inflicted the lesions when this was assumed. This case leads us to suggest that patients with dermatitis artefacta might have comorbid dissociative experiences, which cannot be identified easily.

  4. The relational treatment of dissociative identity disorder.

    PubMed

    Burton, N; Lane, R C

    2001-03-01

    The intent of this paper is to review the literature pertaining to the transference and countertransference components in the treatment of dissociative identity disorder. Aspects of transference and countertransference are presented and discussed within the relational psychoanalytic model. The functions of empathy, enactment, projective identification, and transitional objects are reviewed. Specific attitudes in the transference and countertransference are illuminated and major transference themes are discussed. Finally, a case vignette illustrates some of the central issues involved in the treatment of dissociative identity disorder.

  5. STABILITY OF A SPHERICAL ACCRETION SHOCK WITH NUCLEAR DISSOCIATION

    SciTech Connect

    Fernandez, Rodrigo; Thompson, Christopher

    2009-06-01

    We examine the stability of a standing shock wave within a spherical accretion flow onto a gravitating star, in the context of core-collapse supernova explosions. Our focus is on the effect of nuclear dissociation below the shock on the linear growth, and nonlinear saturation, of nonradial oscillations of the shocked fluid. We combine two-dimensional, time-dependent hydrodynamic simulations using FLASH2.5 with a solution to the linear eigenvalue problem, and demonstrate the consistency of the two approaches. Previous studies of this 'standing accretion shock instability' (SASI) have focused either on zero-energy accretion flows without nuclear dissociation, or made use of a detailed finite-temperature nuclear equation of state and included strong neutrino heating. Our main goal in this and subsequent papers is to introduce equations of state of increasing complexity, in order to isolate the various competing effects. In this work, we employ an ideal gas equation of state with a constant rate of nuclear dissociation below the shock, and do not include neutrino heating. We find that a negative Bernoulli parameter below the shock significantly lowers the real frequency, growth rate, and saturation amplitude of the SASI. A decrease in the adiabatic index has similar effects. The nonlinear development of the instability is characterized by an expansion of the shock driven by turbulent kinetic energy at nearly constant internal energy. Our results also provide further insight into the instability mechanism: the rate of growth of a particular mode is fastest when the radial advection time from the shock to the accretor overlaps with the period of a standing lateral sound wave. The fastest-growing mode can therefore be modified by nuclear dissociation.

  6. Stability of a Spherical Accretion Shock with Nuclear Dissociation

    NASA Astrophysics Data System (ADS)

    Fernández, Rodrigo; Thompson, Christopher

    2009-06-01

    We examine the stability of a standing shock wave within a spherical accretion flow onto a gravitating star, in the context of core-collapse supernova explosions. Our focus is on the effect of nuclear dissociation below the shock on the linear growth, and nonlinear saturation, of nonradial oscillations of the shocked fluid. We combine two-dimensional, time-dependent hydrodynamic simulations using FLASH2.5 with a solution to the linear eigenvalue problem, and demonstrate the consistency of the two approaches. Previous studies of this "standing accretion shock instability" (SASI) have focused either on zero-energy accretion flows without nuclear dissociation, or made use of a detailed finite-temperature nuclear equation of state and included strong neutrino heating. Our main goal in this and subsequent papers is to introduce equations of state of increasing complexity, in order to isolate the various competing effects. In this work, we employ an ideal gas equation of state with a constant rate of nuclear dissociation below the shock, and do not include neutrino heating. We find that a negative Bernoulli parameter below the shock significantly lowers the real frequency, growth rate, and saturation amplitude of the SASI. A decrease in the adiabatic index has similar effects. The nonlinear development of the instability is characterized by an expansion of the shock driven by turbulent kinetic energy at nearly constant internal energy. Our results also provide further insight into the instability mechanism: the rate of growth of a particular mode is fastest when the radial advection time from the shock to the accretor overlaps with the period of a standing lateral sound wave. The fastest-growing mode can therefore be modified by nuclear dissociation.

  7. The tactical-integration model for the treatment of dissociative identity disorder and allied dissociative disorders.

    PubMed

    Fine, C G

    1999-01-01

    The ebb and flow of the diagnosis of Dissociative Identity Disorder (DID) and other dissociative conditions has led to the evolution of theories and treatment modalities to resolve the fluctuating and ephemerous symptoms of these conditions. This paper summarizes the structured cognitive-behavioral-based treatment of dissociative disorders that will foster not only symptom relief but also an integration of the personalities and/or ego states into one mainstream of consciousness. This model of DID therapy is called the tactical integration model; it promotes proficiency over posttraumatic and dissociative symptoms, is collaborative and exploratory, and conveys a consistent message of empowerment to the patient.

  8. Subunit dissociations in natural and recombinant hemoglobins.

    PubMed

    Manning, L R; Jenkins, W T; Hess, J R; Vandegriff, K; Winslow, R M; Manning, J M

    1996-04-01

    A precise and rapid procedure employing gel filtration on Superose-12 to measure the tetramer-dimer dissociation constants of some natural and recombinant hemoglobins in the oxy conformation is described. Natural sickle hemoglobin was chosen to verify the validity of the results by comparing the values with those reported using an independent method not based on gel filtration. Recombinant sickle hemoglobin, as well as a sickle double mutant with a substitution at the Val-6(beta) receptor site, had approximately the same dissociation constant as natural sickle hemoglobin. Of the two recombinant hemoglobins with amino acid replacements in the alpha 1 beta 2 subunit interface, one was found to be extensively dissociated and the other completely dissociated. In addition, the absence of an effect of the allosteric regulators DPG and IHP on the dissociation constant was demonstrated. Thus, a tetramer dissociation constant can now be determined readily and used together with other criteria for characterization of hemoglobins and their interaction with small regulatory molecules. PMID:8845768

  9. Dissociative Ionization of Benzene by Electron Impact

    NASA Technical Reports Server (NTRS)

    Huo, Winifred; Dateo, Christopher; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.

  10. Unimolecular dissociation of cyclopentadiene and indene

    SciTech Connect

    Yi, W.; Chattopadhyay, A.; Bersohn, R. )

    1991-05-01

    The dissociation of hydrogen atoms from the methylene group of cyclopentadiene (CP) and indene (ID) excited with a 193 nm photon has been studied by hydrogen atom laser induced fluorescence. The rate of dissociation of IND was 7.4{times}10{sup 6} s{sup {minus}1} but that of CP was too fast to measure. The ratio of H atoms to D atoms generated from 5-deuteriocyclopentadiene (5-dCP) was 3.91{plus minus}0.46. Rice--Ramsberger--Kassel--Marcus theory was used to calculate the rates of dissociation of CP and 5-dCP. The quantum yield for dissociating H atoms from CP was 0.85{plus minus}0.07. The ejected H atoms have a Maxwell velocity distribution with temperatures which are equal to the vibrational temperatures, 3690 and 2479 K for CP and IND, respectively. The most important result of the work is this confirmation of an earlier finding on a different set of molecules that the translational temperature of the fragments {ital after} the dissociation is equal to the vibrational temperature {ital before} the dissociation. This is explained by the assumption that the motion of the fast, light hydrogen atom is partly decoupled from that of the heavier, slower atoms.

  11. Discriminating among diagnostic categories using the Dissociative Disorders Interview Schedule.

    PubMed

    Ross, Colin A; Ellason, Joan Weathersbee

    2005-04-01

    The Dissociative Disorders Interview Schedule was administered to 1,308 subjects in eight diagnostic categories, including 296 with dissociative identity disorder. The study tested three hypotheses: (1) the Mahalanobis distance between dissociative identity disorder and each of seven other diagnostic categories would be large, (2) the closest diagnostic category to dissociative identity disorder would be dissociative disorder not otherwise specified, and (3) nondissociative diagnostic categories would be closer to each other than any one to dissociative identity disorder. All three hypotheses were confirmed by these data. The findings support the conclusion that dissociative identity disorder is a discrete category or taxon.

  12. Memory for complex emotional material in dissociative identity disorder.

    PubMed

    Barlow, M Rose

    2011-01-01

    Eleven women with dissociative identity disorder (DID) participated in an experiment that included a variety of memory measures. DID participants were faster than a group of 13 female students at producing autobiographical memories in response to cue words. DID participants had difficulty answering detailed questions about a story containing fear compared with a neutral story; the student group did not. The DID group reported experiencing significantly more childhood trauma than did the student group. Effect sizes were moderate to high. This preliminary study uses a broad conceptualization of memory functioning, combining ecologically valid testing with experimental paradigms and addressing the impact of emotion on memory in trauma survivors.

  13. "Trip-Sitting" in the Black Hole: A Netnographic Study of Dissociation and Indigenous Harm Reduction.

    PubMed

    Hearne, Evelyn; Van Hout, Marie Claire

    2016-01-01

    An array of dissociative novel psychoactive substances, including "methoxetamine," "3-MeO-PCP," and "methoxphenidine," have emerged as substitutes for the illicit substance "ketamine." A netographic research methodology aimed to describe online, dissociative novel psychoactive substance users' perceptions of risk, informed knowledge around use, and indigenous harm-reduction practices as advocated within online drug fora, so as to provide credible information which can be used to inform public online health education and drug prevention. Systematic Internet searches were performed using the terms "synthetic dissociative," "methoxetamine," "methoxphenidine," "diphenidine," "3-MeO-PCP," "4-MeO-PCP," "2-MDP," and "dissociative research chemical" in combination with "forum." Following screening of 3,476 forum threads with removal of duplicates and exclusion criteria, 90 user trip reports and 115 fora threads from seven drug fora websites were analyzed by conducting content analysis. Five themes emerged with 43 categories. The findings illustrated how forum activity within the cyber drug user community disseminated and exchanged "communal folk pharmacology" relating to the use of dissociative novel psychoactive substances. Further research and consistent monitoring of Internet drug fora are advised to explore variations in harm-reduction tactics throughout dissociative NPS populations, and to consider how existing harm-reduction initiatives are influencing these hard-to-reach groups.

  14. "Trip-Sitting" in the Black Hole: A Netnographic Study of Dissociation and Indigenous Harm Reduction.

    PubMed

    Hearne, Evelyn; Van Hout, Marie Claire

    2016-01-01

    An array of dissociative novel psychoactive substances, including "methoxetamine," "3-MeO-PCP," and "methoxphenidine," have emerged as substitutes for the illicit substance "ketamine." A netographic research methodology aimed to describe online, dissociative novel psychoactive substance users' perceptions of risk, informed knowledge around use, and indigenous harm-reduction practices as advocated within online drug fora, so as to provide credible information which can be used to inform public online health education and drug prevention. Systematic Internet searches were performed using the terms "synthetic dissociative," "methoxetamine," "methoxphenidine," "diphenidine," "3-MeO-PCP," "4-MeO-PCP," "2-MDP," and "dissociative research chemical" in combination with "forum." Following screening of 3,476 forum threads with removal of duplicates and exclusion criteria, 90 user trip reports and 115 fora threads from seven drug fora websites were analyzed by conducting content analysis. Five themes emerged with 43 categories. The findings illustrated how forum activity within the cyber drug user community disseminated and exchanged "communal folk pharmacology" relating to the use of dissociative novel psychoactive substances. Further research and consistent monitoring of Internet drug fora are advised to explore variations in harm-reduction tactics throughout dissociative NPS populations, and to consider how existing harm-reduction initiatives are influencing these hard-to-reach groups. PMID:27430659

  15. Generating Breathable Air Through Dissociation of N2O

    NASA Technical Reports Server (NTRS)

    Zubrin, Robert; Frankie, Brian

    2006-01-01

    includes one or more "destroyer" subsystems for removing any nitrogen oxides that remain downstream of the main N2O-dissociation reactor. A destroyer includes a carbon bed in series with a catalytic reactor, and is in thermal contact with the main N2O-dissociation reactor. The gas mixture that leaves the main reactor first goes through a carbon bed, which adsorbs all of the trace NO and most of the trace NO2. The gas mixture then goes through the destroyer catalytic reactor, wherein most or all of the remaining NO2 is dissociated. A NOBOSS can be designed to regulate its reactor temperature across a range of flow rates. One such system includes three destroyer loops; these loops act, in combination with a heat sink, to remove heat from the main N2O-dissociation reactor. In this system, the N2O and product gases play an additional role as coolants; thus, as needed, the coolant flow increases in proportion to the rate of generation of heat, helping to keep the main-reactor temperature below 540 C.

  16. Dissociations between developmental dyslexias and attention deficits

    PubMed Central

    Lukov, Limor; Friedmann, Naama; Shalev, Lilach; Khentov-Kraus, Lilach; Shalev, Nir; Lorber, Rakefet; Guggenheim, Revital

    2014-01-01

    We examine whether attention deficits underlie developmental dyslexia, or certain types of dyslexia, by presenting double dissociations between the two. We took into account the existence of distinct types of dyslexia and of attention deficits, and focused on dyslexias that may be thought to have an attentional basis: letter position dyslexia (LPD), in which letters migrate within words, attentional dyslexia (AD), in which letters migrate between words, neglect dyslexia, in which letters on one side of the word are omitted or substituted, and surface dyslexia, in which words are read via the sublexical route. We tested 110 children and adults with developmental dyslexia and/or attention deficits, using extensive batteries of reading and attention. For each participant, the existence of dyslexia and the dyslexia type were tested using reading tests that included stimuli sensitive to the various dyslexia types. Attention deficit and its type was established through attention tasks assessing sustained, selective, orienting, and executive attention functioning. Using this procedure, we identified 55 participants who showed a double dissociation between reading and attention: 28 had dyslexia with normal attention and 27 had attention deficits with normal reading. Importantly, each dyslexia with suspected attentional basis dissociated from attention: we found 21 individuals with LPD, 13 AD, 2 neglect dyslexia, and 12 surface dyslexia without attention deficits. Other dyslexia types (vowel dyslexia, phonological dyslexia, visual dyslexia) also dissociated from attention deficits. Examination of 55 additional individuals with both a specific dyslexia and a certain attention deficit found no attention function that was consistently linked with any dyslexia type. Specifically, LPD and AD dissociated from selective attention, neglect dyslexia dissociated from orienting, and surface dyslexia dissociated from sustained and executive attention. These results indicate that

  17. Dissociable Learning Processes Underlie Human Pain Conditioning

    PubMed Central

    Zhang, Suyi; Mano, Hiroaki; Ganesh, Gowrishankar; Robbins, Trevor; Seymour, Ben

    2016-01-01

    Summary Pavlovian conditioning underlies many aspects of pain behavior, including fear and threat detection [1], escape and avoidance learning [2], and endogenous analgesia [3]. Although a central role for the amygdala is well established [4], both human and animal studies implicate other brain regions in learning, notably ventral striatum and cerebellum [5]. It remains unclear whether these regions make different contributions to a single aversive learning process or represent independent learning mechanisms that interact to generate the expression of pain-related behavior. We designed a human parallel aversive conditioning paradigm in which different Pavlovian visual cues probabilistically predicted thermal pain primarily to either the left or right arm and studied the acquisition of conditioned Pavlovian responses using combined physiological recordings and fMRI. Using computational modeling based on reinforcement learning theory, we found that conditioning involves two distinct types of learning process. First, a non-specific “preparatory” system learns aversive facial expressions and autonomic responses such as skin conductance. The associated learning signals—the learned associability and prediction error—were correlated with fMRI brain responses in amygdala-striatal regions, corresponding to the classic aversive (fear) learning circuit. Second, a specific lateralized system learns “consummatory” limb-withdrawal responses, detectable with electromyography of the arm to which pain is predicted. Its related learned associability was correlated with responses in ipsilateral cerebellar cortex, suggesting a novel computational role for the cerebellum in pain. In conclusion, our results show that the overall phenotype of conditioned pain behavior depends on two dissociable reinforcement learning circuits. PMID:26711494

  18. Dissociable Learning Processes Underlie Human Pain Conditioning.

    PubMed

    Zhang, Suyi; Mano, Hiroaki; Ganesh, Gowrishankar; Robbins, Trevor; Seymour, Ben

    2016-01-11

    Pavlovian conditioning underlies many aspects of pain behavior, including fear and threat detection [1], escape and avoidance learning [2], and endogenous analgesia [3]. Although a central role for the amygdala is well established [4], both human and animal studies implicate other brain regions in learning, notably ventral striatum and cerebellum [5]. It remains unclear whether these regions make different contributions to a single aversive learning process or represent independent learning mechanisms that interact to generate the expression of pain-related behavior. We designed a human parallel aversive conditioning paradigm in which different Pavlovian visual cues probabilistically predicted thermal pain primarily to either the left or right arm and studied the acquisition of conditioned Pavlovian responses using combined physiological recordings and fMRI. Using computational modeling based on reinforcement learning theory, we found that conditioning involves two distinct types of learning process. First, a non-specific "preparatory" system learns aversive facial expressions and autonomic responses such as skin conductance. The associated learning signals-the learned associability and prediction error-were correlated with fMRI brain responses in amygdala-striatal regions, corresponding to the classic aversive (fear) learning circuit. Second, a specific lateralized system learns "consummatory" limb-withdrawal responses, detectable with electromyography of the arm to which pain is predicted. Its related learned associability was correlated with responses in ipsilateral cerebellar cortex, suggesting a novel computational role for the cerebellum in pain. In conclusion, our results show that the overall phenotype of conditioned pain behavior depends on two dissociable reinforcement learning circuits. PMID:26711494

  19. Dissociable Learning Processes Underlie Human Pain Conditioning.

    PubMed

    Zhang, Suyi; Mano, Hiroaki; Ganesh, Gowrishankar; Robbins, Trevor; Seymour, Ben

    2016-01-11

    Pavlovian conditioning underlies many aspects of pain behavior, including fear and threat detection [1], escape and avoidance learning [2], and endogenous analgesia [3]. Although a central role for the amygdala is well established [4], both human and animal studies implicate other brain regions in learning, notably ventral striatum and cerebellum [5]. It remains unclear whether these regions make different contributions to a single aversive learning process or represent independent learning mechanisms that interact to generate the expression of pain-related behavior. We designed a human parallel aversive conditioning paradigm in which different Pavlovian visual cues probabilistically predicted thermal pain primarily to either the left or right arm and studied the acquisition of conditioned Pavlovian responses using combined physiological recordings and fMRI. Using computational modeling based on reinforcement learning theory, we found that conditioning involves two distinct types of learning process. First, a non-specific "preparatory" system learns aversive facial expressions and autonomic responses such as skin conductance. The associated learning signals-the learned associability and prediction error-were correlated with fMRI brain responses in amygdala-striatal regions, corresponding to the classic aversive (fear) learning circuit. Second, a specific lateralized system learns "consummatory" limb-withdrawal responses, detectable with electromyography of the arm to which pain is predicted. Its related learned associability was correlated with responses in ipsilateral cerebellar cortex, suggesting a novel computational role for the cerebellum in pain. In conclusion, our results show that the overall phenotype of conditioned pain behavior depends on two dissociable reinforcement learning circuits.

  20. Dissociative Recombination of Molecular Ions for Astrochemistry

    NASA Astrophysics Data System (ADS)

    Novotny, Oldrich; Becker, A.; Buhr, H.; Fleischmann, Andreas; Gamer, Lisa; Geppert, W.; Krantz, C.; Kreckel, H.; Schwalm, D.; Spruck, K.; Wolf, A.; Savin, Daniel Wolf

    2014-06-01

    Dissociative recombination (DR) of molecular ions is a key chemical process in the cold interstellar medium (ISM). DR affects the composition, charge state, and energy balance of such environments. Astrochemical models of the ISM require reliable total DR cross sections as well as knowledge of the chemical composition of the neutral DR products. We have systematically measured DR for many astrophysically relevant molecular ions utilizing the TSR storage ring at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg, Germany. We used the merged ion-electron beam technique combined with an energy- and position-sensitive imaging detector and are able to study DR down to plasma temperatures as low as 10 K. The DR count rate is used to obtain an absolute merged beams DR rate coefficient from which we can derive a thermal rate coefficient needed for plasma models. Additionally we determine the masses of the DR products by measuring their kinetic energy in the laboratory reference frame. This allows us to assign particular DR fragmentation channels and to obtain their branching ratios. All this information is particularly important for understanding DR of heteronuclear polyatomic ions. We will present DR results for several ions recently investigated at TSR. A new Cryogenic Storage Ring (CSR) is currently being commissioned at MPIK. With the chamber cooled down to ~10 K and a base pressure better than 10-13 mbar, this setup will allow internal cooling of the stored ions down to their rotational ground states, thus opening a new era in DR experiments. New technological challenges arise due to the ultracold, ultra-high vacuum environment of the CSR and thus the detection techniques used at TSR cannot be easily transferred to CSR. We will present new approaches for DR fragment detection in cryogenic environment. This work is supported in part by NASA and the NSF.

  1. Electromagnetic Dissociation and Spacecraft Electronics Damage

    NASA Technical Reports Server (NTRS)

    Norbury, John W.

    2016-01-01

    When protons or heavy ions from galactic cosmic rays (GCR) or solar particle events (SPE) interact with target nuclei in spacecraft, there can be two different types of interactions. The more familiar strong nuclear interaction often dominates and is responsible for nuclear fragmentation in either the GCR or SPE projectile nucleus or the spacecraft target nucleus. (Of course, the proton does not break up, except possibly to produce pions or other hadrons.) The less familiar, second type of interaction is due to the very strong electromagnetic fields that exist when two charged nuclei pass very close to each other. This process is called electromagnetic dissociation (EMD) and primarily results in the emission of neutrons, protons and light ions (isotopes of hydrogen and helium). The cross section for particle production is approximately defined as the number of particles produced in nucleus-nucleus collisions or other types of reactions. (There are various kinematic and other factors which multiply the particle number to arrive at the cross section.) Strong, nuclear interactions usually dominate the nuclear reactions of most interest that occur between GCR and target nuclei. However, for heavy nuclei (near Fe and beyond) at high energy the EMD cross section can be much larger than the strong nuclear interaction cross section. This paper poses a question: Are there projectile or target nuclei combinations in the interaction of GCR or SPE where the EMD reaction cross section plays a dominant role? If the answer is affirmative, then EMD mechanisms should be an integral part of codes that are used to predict damage to spacecraft electronics. The question can become more fine-tuned and one can ask about total reaction cross sections as compared to double differential cross sections. These issues will be addressed in the present paper.

  2. K*-charmonium dissociation cross sections and charmonium dissociation rates in hadronic matter

    NASA Astrophysics Data System (ADS)

    Liu, Feng-Rong; Ji, Shi-Tao; Xu, Xiao-Ming

    2016-08-01

    K*-charmonium dissociation reactions in hadronic matter are studied in the Born approximation, in the quark-interchange mechanism, and with a temperature-dependent quark potential. We obtain the temperature dependence of the unpolarized cross sections for the reactions K^* J/ψ to bar DD_s^ + ,bar D^* D_s^ + ,bar DD_s^{* + } , and bar D^* D_s^{* + } ; K^* χ _c to bar DD_s^ + ,bar D^* D_s^ + ,bar DD_s^{* + } , and bar D^* D_s^{* + } . We use the cross sections for charmonium dissociation in collisions with pions, ρ mesons, kaons, vector kaons, and η mesons to calculate the dissociation rates of charmonium with five types of mesons. Because of the temperature dependence of the meson masses, dissociation cross sections, and meson distribution functions, the charmonium dissociation rates generally increase with increasing temperature and decrease with increasing charmonium momentum from 2.2 GeV/c. We find that the first derivative of the dissociation rate with respect to the charmonium momentum is zero when the charmonium is at rest. While the η + ψ' and the η + χ c dissociation reactions can be neglected, the J/ ψ, ψ', and χ c dissociations are caused by collisions with pions, ρ mesons, kaons, vector kaons, and η mesons.

  3. Dissociation and vulnerability to psychotic experience. The Dissociative Experiences Scale and the MMPI-2.

    PubMed

    Allen, J G; Coyne, L

    1995-10-01

    Prior research on the MMPI has cautioned against misdiagnosing schizophrenia in patients with dissociative identity disorder. The present study examined the full spectrum of the dissociative experience in relation to MMPI-2 profiles. Ninety-eight women in treatment for trauma-related disorders completed the Dissociative Experiences Scale and the MMPI-2 in routine inpatient diagnostic evaluations. Consistent with prior research, severe dissociation was associated with high elevations on MMPI-2 scales typically associated with psychotic symptoms. Contrary to hypotheses, the ostensibly most benign form of dissociation, absorption and imaginative involvement, was somewhat more strongly related to MMPI-2 scores than the more pathognomonic forms of dissociation, depersonalization and amnesia. Although it should not be misdiagnosed, severe impairment on the MMPI in conjunction with dissociation should be taken seriously as suggesting vulnerability to psychotic experience. The dissociative retreat from the stressors of outer reality opens the door to the inner world of traumatic images and affects, along with compromised reality testing and disorganized thinking.

  4. Dissociation in borderline personality disorder: a detailed look.

    PubMed

    Korzekwa, Marilyn I; Dell, Paul F; Links, Paul S; Thabane, Lehana; Fougere, Philip

    2009-01-01

    The objective of the present study was to assess in detail the whole spectrum of normal and pathological dissociative experiences and dissociative disorder (DD) diagnoses in borderline personality disorder (BPD) as diagnosed with the Revised Diagnostic Interview for Borderlines. Dissociation was measured comprehensively in 21 BPD outpatients using the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised, the Multidimensional Inventory of Dissociation (MID), the Dissociative Experiences Scale pathological taxon analysis, and the Somatoform Dissociation Questionnaire. The frequencies of DDs in this BPD sample were as follows: 24% no DD, 29% mild DD (dissociative amnesia and depersonalization disorder), 24% DD Not Otherwise Specified (DDNOS), and 24% dissociative identity disorder. With regard to the dissociative experiences endorsed, almost all patients reported identity confusion, unexplained mood changes, and depersonalization. Even those BPD patients with mild DD reported derealization, depersonalization, and dissociative amnesia. BPD patients with DDNOS reported frequent depersonalization, frequent amnesia, and notable experiences of identity alteration. BPD patients with dissociative identity disorder endorsed severe dissociative symptoms in all categories. Analysis of the MID pathological dissociation items revealed that 32% of the items were endorsed at a clinically significant level of frequency by more than 50% of our BPD patients. In conclusion, the frequencies of Diagnostic and Statistical Manual of Mental Disorders (4th ed.) DDs in these patients with BPD were surprisingly high. Likewise, the "average" BPD patient endorsed a wide variety of recurrent pathological dissociative symptoms.

  5. Isotope separation by photoselective dissociative electron capture

    DOEpatents

    Stevens, Charles G. [Pleasanton, CA

    1978-08-29

    A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, .sup.235 UF.sub.6 is separated from a UF.sub.6 mixture by selective excitation followed by dissociative electron capture into .sup.235 UF.sub.5 - and F.

  6. Isotope separation by photoselective dissociative electron capture

    DOEpatents

    Stevens, C.G.

    1978-08-29

    Disclosed is a method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, [sup 235]UF[sub 6] is separated from a UF[sub 6] mixture by selective excitation followed by dissociative electron capture into [sup 235]UF[sub 5]- and F. 2 figs.

  7. Dissociating motor cortex from the motor

    PubMed Central

    Schieber, Marc H

    2011-01-01

    Abstract During closed-loop control of a brain–computer interface, neurons in the primary motor cortex can be intensely active even though the subject may be making no detectable movement or muscle contraction. How can neural activity in the primary motor cortex become dissociated from the movements and muscles of the native limb that it normally controls? Here we examine circumstances in which motor cortex activity is known to dissociate from movement – including mental imagery, visuo-motor dissociation and instructed delay. Many such motor cortex neurons may be related to muscle activity only indirectly. Furthermore, the integration of thousands of synaptic inputs by individual α-motoneurons means that under certain circumstances even cortico-motoneuronal cells, which make monosynaptic connections to α-motoneurons, can become dissociated from muscle activity. The natural ability of motor cortex neurons under voluntarily control to become dissociated from bodily movement may underlie the utility of this cortical area for controlling brain–computer interfaces. PMID:22005673

  8. Ion-induced dissociation dynamics of acetylene

    SciTech Connect

    De, Sankar; Rajput, Jyoti; Roy, A.; Safvan, C. P.; Ghosh, P. N.

    2008-02-15

    We report on the results of dissociation dynamics of multiple charged acetylene molecules formed in collision with 1.2 MeV Ar{sup 8+} projectiles. Using the coincidence map, we can separate out the different dissociation pathways between carbon and hydrogen ionic fragments as well as complete two-body breakup events. From the measured slopes of the coincidence islands for carbon atomic fragments and theoretical values determined from the charge and momentum distribution of the correlated particles, we observe a diatom like behavior of the C-C charged complex during dissociation of multiply charged C{sub 2}H{sub 2}. We conclude that this behavior in breakup dynamics is a signature of sequentiality in dissociation of this multiply charged molecular species. The shape and orientation of the islands give further information about the momentum balance in the fragmentation process of two- or many-body dissociation pathways. Kinetic energy release of different breakup channels are reported here and compared with values calculated from the pure Coulomb explosion model.

  9. Incrementally Dissociating Syntax and Semantics

    ERIC Educational Resources Information Center

    Brennan, Jonathan R.

    2010-01-01

    A basic challenge for research into the neurobiology of language is understanding how the brain combines words to make complex representations. Linguistic theory divides this task into several computations including syntactic structure building and semantic composition. The close relationship between these computations, however, poses a strong…

  10. Effective Rho-associated protein kinase inhibitor treatment to dissociate human iPS cells for suspension culture to form embryoid body-like cell aggregates.

    PubMed

    Horiguchi, Ayumi; Yazaki, Koyuki; Aoyagi, Mami; Ohnuki, Yoshitsugu; Kurosawa, Hiroshi

    2014-11-01

    Treatment conditions using Y-27632 in the preparation of cell suspension of dissociated human pluripotent stem cells (hiPSCs) were investigated in the context of embryoid body (EB)-like cell aggregates. The effectiveness of a pretreatment with Y-27632 before cell dissociation and that of a Y-27632 treatment during cell dissociation were investigated from the viewpoint of simplicity and robustness. The duration of Y-27632 treatment in the preparation process affected the circularity and agglomeration of dissociated hiPSCs. A single application of pretreatment failed to prevent the onset of blebbing. However, a pretreatment promoted the agglomeration of dissociated hiPSCs when combined with the addition of Y-27632 to cell suspension. Our results indicate that pretreatment enhances the agglomeration potential of dissociated hiPSCs. When cell dissociation was performed in the presence of Y-27632, dissociated hiPSCs possessed the highest circularity and significant agglomerating property. It was shown that treatment with Y-27632 during cell dissociation is a simple and robust method to prepare dissociated hiPSCs for suspension culture to form EB-like cell aggregates.

  11. Dissociation in virtual reality: depersonalization and derealization

    NASA Astrophysics Data System (ADS)

    Garvey, Gregory P.

    2010-01-01

    This paper looks at virtual worlds such as Second Life7 (SL) as possible incubators of dissociation disorders as classified by the Diagnostic and Statistical Manual of Mental Disorders, 4th Edition3 (also known as the DSM-IV). Depersonalization is where "a person feels that he or she has changed in some way or is somehow unreal." Derealization when "the same beliefs are held about one's surroundings." Dissociative Identity Disorder (DID), previously known as multiple personality disorder fits users of Second Life who adopt "in-world" avatars and in effect, enact multiple distinct identities or personalities (known as alter egos or alters). Select questions from the Structured Clinical Interview for Depersonalization (SCI-DER)8 will be discussed as they might apply to the user's experience in Second Life. Finally I would like to consider the hypothesis that rather than a pathological disorder, dissociation is a normal response to the "artificial reality" of Second Life.

  12. Electron Transfer Dissociation of Oligonucleotide Cations.

    PubMed

    Smith, Suncerae I; Brodbelt, Jennifer S

    2009-06-01

    Electron transfer dissociation (ETD) of multi-protonated 6 - 20-mer oligonucleotides and 12- and 14-mer duplexes is compared to collision activated dissociation (CAD). ETD causes efficient charge reduction of the multi-protonated oligonucleotides in addition to limited backbone cleavages to yield sequence ions of low abundance. Subsequent CAD of the charge-reduced oligonucleotides formed upon electron transfer, in a net process termed electron transfer collision activated dissociation (ETcaD), results in rich fragmentation in terms of w, a, z, and d products, with a marked decrease in the abundance of base loss ions and internal fragments. Complete sequencing was possible for nearly all oligonucleotides studied. ETcaD of an oligonucleotide duplex resulted in specific backbone cleavages, with conservation of weaker non-covalent bonds. PMID:20161288

  13. Charge Prediction Machine: A tool for inferring precursor charge states of Electron Transfer Dissociation tandem mass spectra

    PubMed Central

    Carvalho, Paulo C; Cociorva, Daniel; Wong, Catherine; Carvalho, Maria da Gloria da C; Barbosa, Valmir C; Yates, John R

    2010-01-01

    Electron Transfer Dissociation (ETD) can dissociate highly charged ions. Efficient analysis of ions dissociated with ETD requires accurate determination of charge states for calculation of molecular weight. We created an algorithm to assign the charge state of ions often used for ETD. The program, Charge Prediction Machine (CPM), uses Bayesian decision theory to account for different charge reduction processes encountered in ETD, and can also handle multiplex spectra. CPM correctly assigned charge states to 98% of the 13,097 MS2 spectra from a combined dataset of four experiments. In a comparison between CPM and a competing program, Charger (ThermoFisher), CPM produced half the mistakes. PMID:19203245

  14. Psychotherapy and pharmacotherapy for patients with dissociative identity disorder.

    PubMed

    Gentile, Julie P; Dillon, Kristy S; Gillig, Paulette Marie

    2013-02-01

    There is a wide variety of what have been called "dissociative disorders," including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and forms of dissociative disorder not otherwise specified. Some of these diagnoses, particularly dissociative identity disorder, are controversial and have been questioned by many clinicians over the years. The disorders may be under-diagnosed or misdiagnosed, but many persons who have experienced trauma report "dissociative" symptoms. Prevalence of dissociative disorders is unknown, but current estimates are higher than previously thought. This paper reviews clinical, phenomenological, and epidemiological data regarding diagnosis in general, and illustrates possible treatment interventions for dissociative identity disorder, with a focus on psychotherapy interventions and a review of current psychopharmacology recommendations as part of a comprehensive multidisciplinary treatment plan. PMID:23556139

  15. Psychotherapy and pharmacotherapy for patients with dissociative identity disorder.

    PubMed

    Gentile, Julie P; Dillon, Kristy S; Gillig, Paulette Marie

    2013-02-01

    There is a wide variety of what have been called "dissociative disorders," including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and forms of dissociative disorder not otherwise specified. Some of these diagnoses, particularly dissociative identity disorder, are controversial and have been questioned by many clinicians over the years. The disorders may be under-diagnosed or misdiagnosed, but many persons who have experienced trauma report "dissociative" symptoms. Prevalence of dissociative disorders is unknown, but current estimates are higher than previously thought. This paper reviews clinical, phenomenological, and epidemiological data regarding diagnosis in general, and illustrates possible treatment interventions for dissociative identity disorder, with a focus on psychotherapy interventions and a review of current psychopharmacology recommendations as part of a comprehensive multidisciplinary treatment plan.

  16. Blackbody Infrared Radiative Dissociation of Protonated Oligosaccharides

    NASA Astrophysics Data System (ADS)

    Fentabil, Messele A.; Daneshfar, Rambod; Kitova, Elena N.; Klassen, John S.

    2011-12-01

    The dissociation pathways, kinetics, and energetics of protonated oligosaccharides in the gas phase were investigated using blackbody infrared radiative dissociation (BIRD). Time-resolved BIRD measurements were performed on singly protonated ions of cellohexaose (Cel6), which is composed of β-(1 → 4)-linked glucopyranose rings, and five malto-oligosaccharides (Malx, where x = 4-8), which are composed of α-(1 → 4)-linked glucopyranose units. At the temperatures investigated (85-160 °C), the oligosaccharides dissociate at the glycosidic linkages or by the loss of a water molecule to produce B- or Y-type ions. The Y ions dissociate to smaller Y or B ions, while the B ions yield exclusively smaller B ions. The sequential loss of water molecules from the smallest B ions (B1 and B2) also occurs. Rate constants for dissociation of the protonated oligosaccharides and the corresponding Arrhenius activation parameters (Ea and A) were determined. The Ea and A-factors measured for protonated Malx (x > 4) are indistinguishable within error (~19 kcal mol-1, 1010 s-1), which is consistent with the ions being in the rapid energy exchange limit. In contrast, the Arrhenius parameters for protonated Cel6 (24 kcal mol-1, 1012 s-1) are significantly larger. These results indicate that both the energy and entropy changes associated with the glycosidic bond cleavage are sensitive to the anomeric configuration. Based on the results of this study, it is proposed that formation of B and Y ions occurs through a common dissociation mechanism, with the position of the proton establishing whether a B or Y ion is formed upon glycosidic bond cleavage.

  17. Swirling flow of a dissociated gas

    NASA Technical Reports Server (NTRS)

    Wolfram, W. R., Jr.; Walker, W. F.

    1975-01-01

    Most physical applications of the swirling flow, defined as a vortex superimposed on an axial flow in the nozzle, involve high temperatures and the possibility of real gas effects. The generalized one-dimensional swirling flow in a converging-diverging nozzle is analyzed for equilibrium and frozen dissociation using the ideal dissociating gas model. Numerical results are provided to illustrate the major effects and to compare with results obtained for a perfect gas with constant ratio of specific heats. It is found that, even in the case of real gases, perfect gas calculations can give a good estimate of the reduction in mass flow due to swirl.

  18. Quantum Zeno control of coherent dissociation

    SciTech Connect

    Khripkov, C.; Vardi, A.

    2011-08-15

    We study the effect of dephasing on the coherent dissociation dynamics of an atom-molecule Bose-Einstein condensate. We show that when phase-noise intensity is strong with respect to the inverse correlation time of the stimulated process, dissociation is suppressed via a Bose enhanced quantum Zeno effect. This is complementary to the quantum Zeno control of phase-diffusion in a bimodal condensate by symmetric noise [Phys. Rev. Lett. 100, 220403 (2008)] in that the controlled process here is phase formation and the required decoherence mechanism for its suppression is purely phase noise.

  19. Dissociation and recombination in an inhomogeneous gas

    NASA Astrophysics Data System (ADS)

    Kuščer, Ivan

    1991-09-01

    The system of Boltzmann equations of Ludwig and Heil for a dissociating gas mixture is reviewed and reformulated in terms of differential cross sections. For the purpose of Monte Carlo simulations, collision models of the type of Borgnakke and Larsen are proposed. In case of short-lived transient flows of molecular gases and at not too high temperatures, simulation of scattering collisions is expected to suffice; the distribution function of the dissociated particles can be evaluated afterwards by integration, and recombination can be ignored.

  20. Identity and Introject in dissociative disorders.

    PubMed

    Alpher, V S

    1996-12-01

    The structural analysis of social behavior (SASB) shows promise for systematically examining identity issues in clinical populations. In this study, identity is assessed with the SASB in a sample of women with dissociative disorder (n = 25) and a nonpatient clinical contrast group (n = 25). The SASB Introject--a multivariate measure of identity--effectively differentiated the 2 samples. Despite greater self-directed hostility than the clinical contrast group, dissociative disorder patients showed lower levels of intrapsychic conflict. Implications for further research on identity and psychopathology are discussed.

  1. Dissociative identity disorder: a literature review.

    PubMed

    McAllister, M M

    2000-01-01

    This paper presents a review of the literature into dissociative identity disorder. This disorder, previously known as multiple personality disorder, is increasingly diagnosed, in part because of more focused diagnostic tools, but also because people are accessing services to assist with the longterm problems of early child abuse and neglect. Dissociative identity disorder is examined in the literature according to a variety of discourses, each of which suggest different ways of conceptualizing problems and therapeutic approaches. These discourses reviewed include: psychiatry, psychology, corporeality, feminism, social constructivism, anthropology, and postmodernism. The paper concludes with an examination of the nursing literature and suggests opportunities for nursing research into this complex mental health problem.

  2. The use of hypnosis with dissociative disorders.

    PubMed

    Kluft, R P

    1992-01-01

    The dissociative disorders are characterized by difficulties in the integration of memory and/or identity. Typically this is manifested by amnesia and either the development of alternate identities or an estrangement from one's own identity. Spontaneous and self-generated dissociative states and phenomena sharing much in common with those that can be induced with hypnosis are thought to play a major role in their development, symptomatology, and perpetuation. Medical heterohypnosis offers a powerful tool to reestablish a functional continuity of memory and identity in many such cases. The application of hypnotic interventions in the treatment of such conditions will be discussed, explored, and illustrated with clinical vignettes.

  3. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

    NASA Astrophysics Data System (ADS)

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

    2016-08-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

  4. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization.

    PubMed

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P

    2016-10-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting. Graphical Abstract ᅟ. PMID:27582116

  5. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

    NASA Astrophysics Data System (ADS)

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

    2016-10-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

  6. Dissociative detachment and memory impairment: reversible amnesia or encoding failure?

    PubMed

    Allen, J G; Console, D A; Lewis, L

    1999-01-01

    The authors propose that clinicians endeavor to differentiate between reversible and irreversible memory failures in patients with dissociative symptoms who report "memory gaps" and "lost time." The classic dissociative disorders, such as dissociative amnesia and dissociative identity disorder, entail reversible memory failures associated with encoding experience in altered states. The authors propose another realm of memory failures associated with severe dissociative detachment that may preclude the level of encoding of ongoing experience needed to support durable autobiographical memories. They describe how dissociative detachment may be intertwined with neurobiological factors that impair memory, and they spell out the significance of distinguishing reversible and irreversible memory impairment for diagnosis, patient education, psychotherapy, and research.

  7. Self-destructive behavior in patients with dissociative disorders.

    PubMed

    Saxe, Glenn N; Chawla, Neharika; Van der Kolk, Bessel

    2002-01-01

    Highrates of self-injury have been reported in patients with dissociative disorders, yet no prior study has directly compared these patients with other psychiatric patients. The present study assesses self-destructive behavior in a group of inpatients who have dissociative disorders compared to those who report few dissociative symptoms. These patients more frequently engage in self-destructive behaviors, use more methods of self-injury, and begin to injure themselves at an earlier age then patients who do not dissociate. Results have important implications for understanding the relationship between dissociation, childhood trauma, and self-injury and for assessment and treatment of patients with dissociative disorders.

  8. Carbon monoxide dissociative attachment and resonant dissociation by electron-impact

    NASA Astrophysics Data System (ADS)

    Laporta, V.; Tennyson, J.; Celiberto, R.

    2016-02-01

    Low-energy dissociative electron attachment and resonant electron impact dissociation of CO molecule are considered. Ro-vibrationally resolved cross sections and rate coefficients for both the processes are calculated using an ab-initio model based on the low-lying \\text{X}{{}2}\\Pi resonance of CO-. Final results show that the cross sections increases very rapidly as a function of the ro-vibrational level; these cross sections should be useful for understanding kinetic dissociation of CO in strongly non-equilibrium plasmas.

  9. Dissociative and double photoionization of CO2 from threshold to 90 A

    NASA Technical Reports Server (NTRS)

    Masuoka, T.; Samson, J. A. R.

    1979-01-01

    The molecular photoionization, dissociative photoionization and double photoionization cross sections for CO2 were measured from their onsets down to 90 A by using various combinations of mass spectrometers (a coincidence time-of-flight mass spectrometer and a magnetic mass spectrometer) and light sources (synchrotron radiation, and glow and spark discharge). It is concluded that the one broad peak and the three shoulders in the total adsorption cross section curve between 640 and 90 A are caused completely by dissociative ionization processes. Several peaks observed in the cross section curve for the total fragmentation CO(+)3, O(+) and C(+) are compared with those in the photoelectron spectrum reported for CO2.

  10. Double Dissociation between Reading and Spelling Deficits

    ERIC Educational Resources Information Center

    Moll, Kristina; Landerl, Karin

    2009-01-01

    In two studies dissociations between reading and spelling skills were examined. Study 1 reports equally high prevalence rates for isolated deficits in reading (7%) or spelling (6%) in a representative sample (N = 2,029) of German-speaking elementary school children. In Study 2, children with isolated deficits were presented with the same words to…

  11. Dispelling confusion about traumatic dissociative amnesia.

    PubMed

    McNally, Richard J

    2007-09-01

    How survivors of trauma remember--or forget--their most terrifying experiences lies at the core of one of the most bitter controversies in psychiatry and psychology: the debate regarding repressed memories of childhood sexual abuse. Most experts hold that traumatic events--those experienced as overwhelmingly terrifying and often life-threatening--are remembered very well; however, traumatic dissociative amnesia theorists disagree. Although acknowledging that traumatic events are usually memorable, these theorists nevertheless claim that a sizable minority of survivors are incapable of remembering their trauma. That is, the memory is stored but dissociated (or "repressed") from awareness. However, the evidence that these theorists adduce in support of the concept of traumatic dissociative amnesia is subject to other, more plausible interpretations. The purpose of this review is to dispel confusion regarding the controversial notion of dissociated (or repressed) memory for trauma and to show how people can recall memories of long-forgotten sexual abuse without these memories first having been repressed.

  12. EVIDENCE FOR CO DISSOCIATION ON RHODIUM SURFACES

    SciTech Connect

    Castner, D.G.; Dubois, L.H.; Sexton, B.A.; Somorjai, G.A.

    1980-06-01

    Carbon monoxide adsorbs molecularly on rhodium surfaces at 300K, but if the rhodium samples are heated in the presence of carbon monoxide, there is evidence for carbon-oxygen bond breaking at step and/or defect sites. The effects of step and defect site density, subsurface oxygen concentration, and oxygen dissolution into the rhodium lattice on CO dissociation are discussed.

  13. Subliminal processes, dissociation and the 'I'.

    PubMed

    Bob, Petr

    2003-06-01

    The study of unconscious processes leads to the hypothesis of the limit of consciousness, which involves two main kinds of psychic activity. The first represents psychic contents which are subliminal for their low energy, the second subliminal contents which are inaccessible to consciousness because they are dissociated in the subliminal region. Dissociation is a concept introduced by Pierre Janet for splitting consciousness due to traumatic events or during hypnosis. It takes a more general form in Hilgard's neo-dissociation theory of hypnotic phenomena and also in Jung's theory of the collective unconscious. Further generalization links it to the modern findings of explicit and implicit perception, leading to a shift in dissociation from hypothesis to clinical, experimental and theoretical reality. Studies in hypnosis also point to the existence of an integrative psychic entity, that comprises the conscious 'I'. Hilgard called this the hidden observer, and his findings represent empirical confirmation of Jung's term for the Self as mirror 'I', which leads to many important consequences for self-discovery and the meaning of life.

  14. Process Dissociation and Mixture Signal Detection Theory

    ERIC Educational Resources Information Center

    DeCarlo, Lawrence T.

    2008-01-01

    The process dissociation procedure was developed in an attempt to separate different processes involved in memory tasks. The procedure naturally lends itself to a formulation within a class of mixture signal detection models. The dual process model is shown to be a special case. The mixture signal detection model is applied to data from a widely…

  15. Psychometric properties of the Dissociative Experiences Scale.

    PubMed

    Dubester, K A; Braun, B G

    1995-04-01

    The test-retest reliability of the Dissociative Experiences Scale (DES; Bernstein EM, Putnam FW [1986] Development, reliability, and validity of a dissociation scale. The Journal of Nervous and Mental Disease 174:727-735) in a clinical sample was found to be .93 for the total DES score and .95, .89, and .82 for the three subscale scores of amnesia, depersonalization-derealization, and absorption (dissociative identity disorder [DID], DSM-IV), respectively. Test-retest reliabilities within diagnostic groups of multiple personality disorder, dissociative disorder not otherwise specified, and a general other category of psychiatric diagnoses were obtained for total and subscale scores on the DES. These ranged from .78 to .96. Tests of mean scores across the two test sessions showed the total and subscale scores to be temporally stable. The DES was also found to be highly internally consistent: Cronbach's alphas of .96 and .97 were observed for the total DES scores taken at times 1 and 2, respectively. Construct validity of the DES was demonstrated by differentiation among the subscale scores in a repeated-measures analysis of variance (F[2,154] = 32.03, p < or = .001). Normality and general distribution issues were also addressed and provided a rationale for using the DES with parametric statistics. Reasons why the DES (as it was originally designed) is not appropriate as a dependent measure in outcome research are discussed, along with needed future research. Implications of the findings for the clinical usefulness of the DES as a diagnostic instrument are noted.

  16. Thermal dissociation of copper chalcogenides during melting

    NASA Astrophysics Data System (ADS)

    Pavlova, L. M.; Glazov, V. M.; Asryan, A. A.

    1998-01-01

    An attempt was undertaken to describe the mechanism of dissociation of copper chalcogenides during melting. Two-stage schemes of the dissociation of the Cu2BVI compounds (BVI is S, Se, or Te) were proposed. It was suggested that in the copper-sulfur and copper-selenium melts, Cu2BVI and CuBVI associates exist, whereas in the copper tellurium systems, Cu2Te and Cu5Te3 associates exist. The interpretation of available data on magnetic susceptibility was given in terms of suggested associates in Cu-Te alloys. Nous avons essayé de décrire le mécanisme de dissociation des chalcogénures de cuivre pendant la fusion. Nous proposons des schémas à deux étapes de dissociation pour les composés Cu2BVI (BVI est S, Se, ou Te). Nous suggérons l'existence dans le bain fondu cuivre-soufre et cuivre-sélénium des associés du type Cu2BVI et CuBVI et dans le système cuivre-tellure Cu2Te et Cu5Te3. L'interprétation des données disponibles de susceptibilité magnétique est réalisée en termes de formation d'associés dans les alliages Cu-Te.

  17. Dissociation of carbonic acid: gas phase energetics and mechanism from ab initio metadynamics simulations.

    PubMed

    Kumar, P Padma; Kalinichev, Andrey G; Kirkpatrick, R James

    2007-05-28

    A comprehensive metadynamics study of the energetics, stability, conformational changes, and mechanism of dissociation of gas phase carbonic acid, H2CO3, yields significant new insight into these reactions. The equilibrium geometries, vibrational frequencies, and conformer energies calculated using the density functional theory are in good agreement with the previous theoretical predictions. At 315 K, the cis-cis conformer has a very short life time and transforms easily to the cis-trans conformer through a change in the O=C-O-H dihedral angle. The energy difference between the trans-trans and cis-trans conformers is very small (approximately 1 kcal/mol), but the trans-trans conformer is resistant to dissociation to carbon dioxide and water. The cis-trans conformer has a relatively short path for one of its hydroxyl groups to accept the proton from the other end of the molecule, resulting in a lower activation barrier for dissociation. Comparison of the free and potential energies of dissociation shows that the entropic contribution to the dissociation energy is less than 10%. The potential energy barrier for dissociation of H2CO3 to CO2 and H2O from the metadynamics calculations is 5-6 kcal/mol lower than in previous 0 K studies, possibly due to a combination of a finite temperature and more efficient sampling of the energy landscape in the metadynamics calculations. Gas phase carbonic acid dissociation is triggered by the dehydroxylation of one of the hydroxyl groups, which reorients as it approaches the proton on the other end of the molecule, thus facilitating a favorable H-O-H angle for the formation of a product H2O molecule. The major atomic reorganization of the other part of the molecule is a gradual straightening of the O=C=O bond. The metadynamics results provide a basis for future simulation of the more challenging carbonic acid-water system.

  18. Electromagnetic dissociation of relativistic {sup 28}Si by nucleon emission

    SciTech Connect

    Sonnadara, U.J.

    1992-12-01

    A detailed study of the electromagnetic dissociation of {sup 28}Si by nucleon emission at E{sub lab}/A = 14.6 (GeV/nucleon was carried out with {sup 28}Si beams interacting on {sup 208}Pb). {sup 120}Sn. {sup 64}C targets. The measurements apparatus consists of detectors in the target area which measure the energy and charged multiplicity, and a forward spectrometer which measures the position, momentum and energy of the reaction fragments. The exclusive electromagnetic dissociation cross sections for decay channels having multiple nucleons in the final state have been measured which enables the selection of events produced in pure electromagnetic interactions. The measured cross sections agree well with previous measurements obtained for the removal of a few nucleons as well as with measurements on total charge removal cross sections from other experiments. The dependence of the integrated cross sections on the target charge Z{sub T} and the target mass AT confirms that for higher Z targets the excitation is largely electromagnetic. Direct measurements of the excitation energy for the electromagnetic dissociation of {sup 28}Si {yields} p+{sup 27}Al and {sup 28}Si {yields} n+{sup 27}Si have been obtained through a calculation of the invariant mass in kinematically, reconstructed events. The excitation energy spectrum for all targets peak near the isovector giant dipole resonance in {sup 28}Si. These distributions are well reproduced by combining the photon spectrum calculated using the Weizsaecker-Williams approximation with the experimental data on the photonuclear {sup 28}Si({sub {gamma},p}){sup 27}Al and {sup 28}Si({sub {gamma},n}){sup 27}Si. The possibilities of observing double giant dipole resonance excitations in {sup 28}Si have been investigated with cross section measurements as well as with excitation energy reconstruction.

  19. Electromagnetic dissociation of relativistic [sup 28]Si by nucleon emission

    SciTech Connect

    Sonnadara, U.J.

    1992-12-01

    A detailed study of the electromagnetic dissociation of [sup 28]Si by nucleon emission at E[sub lab]/A = 14.6 (GeV/nucleon was carried out with [sup 28]Si beams interacting on [sup 208]Pb). [sup 120]Sn. [sup 64]C targets. The measurements apparatus consists of detectors in the target area which measure the energy and charged multiplicity, and a forward spectrometer which measures the position, momentum and energy of the reaction fragments. The exclusive electromagnetic dissociation cross sections for decay channels having multiple nucleons in the final state have been measured which enables the selection of events produced in pure electromagnetic interactions. The measured cross sections agree well with previous measurements obtained for the removal of a few nucleons as well as with measurements on total charge removal cross sections from other experiments. The dependence of the integrated cross sections on the target charge Z[sub T] and the target mass AT confirms that for higher Z targets the excitation is largely electromagnetic. Direct measurements of the excitation energy for the electromagnetic dissociation of [sup 28]Si [yields] p+[sup 27]Al and [sup 28]Si [yields] n+[sup 27]Si have been obtained through a calculation of the invariant mass in kinematically, reconstructed events. The excitation energy spectrum for all targets peak near the isovector giant dipole resonance in [sup 28]Si. These distributions are well reproduced by combining the photon spectrum calculated using the Weizsaecker-Williams approximation with the experimental data on the photonuclear [sup 28]Si([sub [gamma],p])[sup 27]Al and [sup 28]Si([sub [gamma],n])[sup 27]Si. The possibilities of observing double giant dipole resonance excitations in [sup 28]Si have been investigated with cross section measurements as well as with excitation energy reconstruction.

  20. Experimental Dissociation of Methane Hydrates Through Depressurization

    NASA Astrophysics Data System (ADS)

    Borgfeldt, T.; Flemings, P. B.; Meyer, D.; You, K.

    2015-12-01

    We dissociated methane hydrates by stepwise depressurization. The initial hydrates were formed by injecting gas into a cylindrical sample of brine-saturated, coarse-grained sand at hydrate-stable conditions with the intention of reaching three-phase equilibrium. The sample was initially at 1°C with a pore pressure of 1775 psi and a salinity of 7 wt. % NaBr. The depressurization setup consisted of one pump filled with tap water attached to the confining fluid port and a second pump attached to the inlet port where the methane was injected. Depressurization was conducted over sixteen hours at a constant temperature of 1°C. The pore pressure was stepwise reduced from 1775 psi to atmospheric pressure by pulling known volumes of gas from the sample. After each extraction, we recorded the instantaneous and equilibrium pore pressure. 0.503 moles of methane were removed from the sample. The pore pressure decreased smoothly and nonlinearly with the cumulative gas withdrawn from the sample. We interpret that hydrate began to dissociate immediately with depressurization, and it continued to dissociate when the pressure decreased below the three-phase pressure for 1°C and 0 wt. % salinity. Two breaks in slope in the pressure vs. mass extracted data are bounded by smooth, nonlinear curves with differing slopes on either side. We attribute the breaks to dissociation of three zones of hydrate concentration. We created a box model to simulate the experimental behavior. For a 10% initial gas saturation (estimated from the hydrate formation experiment and based on mass conservation), an initial hydrate saturation of 55% is required to match the total methane extracted from the sample. Future experiments will be conducted over a longer timespan while monitoring hydrate dissociation with CT imaging throughout the process.

  1. The H2 dissociation on the BN, AlN, BP and AlP nanotubes: a comparative study.

    PubMed

    Beheshtian, Javad; Soleymanabadi, Hamed; Kamfiroozi, Mohammad; Ahmadi, Ali

    2012-06-01

    The thermodynamic and kinetic feasibility of H(2) dissociation on the BN, AlN, BP and AlP zigzag nanotubes has been investigated theoretically by calculating the dissociation and activation energies. We determined the BN and AlP tubes to be inert toward H(2) dissociation, both thermodynamically and kinetically. The reactions are endothermic by 5.8 and 3 kcal mol(-1), exhibiting high activation energies of 38.8 and 30.6 kcal mol(-1), respectively. Our results indicated that H(2) dissociation is thermodynamically favorable on both PB and AlN nanotubes. However, in spite of the thermodynamic feasibility of H(2) dissociation on PB types, this process is kinetically unfavorable due to partly high activation energy. Generally, we concluded that among the four studied tubes, the AlN nanotube may be an appropriate model for H(2) dissociation process, from a thermodynamic and kinetic stand point. We also indicated that H(2) dissociation is not homolytic, rather it takes place via a heterolytic bond cleavage. In addition, a comparative study has been performed on the electrical and geometrical properties of the tubes. Our analysis showed that the electrical conductivity of tubes is as follows: BP>AlP>BN>AlN depending on how to combine the electron rich and electron poor atoms. PMID:21979405

  2. Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates

    SciTech Connect

    Kwon, T.H.; Kneafsey, T.J.; Rees, E.V.L.

    2011-02-15

    Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO{sub 2}) and/or production of methane (CH{sub 4}) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH{sub 4} and CO{sub 2} hydrate (CH{sub 4}-CO{sub 2} mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH{sub 4}-CO{sub 2} mixed hydrates. We prepared CH{sub 4}-CO{sub 2} mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociation of a CH{sub 4}-CO{sub 2} mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH{sub 4}-CO{sub 2} compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO{sub 2} concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO{sub 2} than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO{sub 2} in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO{sub 2} concentration in the vapor phase enriched the hydrate in CO{sub 2}. The dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate lays between the limiting values of pure CH{sub 4} hydrate and CO{sub 2} hydrate, increasing with the CO{sub 2} fraction in the hydrate phase.

  3. A molecular dynamics study of melting and dissociation of tungsten nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Min; Wang, Jun; Fu, Baoqin; Hou, Qing

    2015-12-01

    Molecular dynamics simulations were conducted to study the melting and dissociation of free tungsten nanoparticles. For the various interatomic potentials applied, the melting points of the tungsten nanoparticles increased with increasing nanoparticle diameter. Combining these results with the melting point of bulk tungsten in the experiment, the melting point of nanoparticles with diameters ranging from 4 to 12 nm could be determined. As the temperature increases, free nanoparticles are subject to dissociation phenomena. The dissociation rate was observed to follow Arrhenius behavior, and the Meyer-Neldel rule was obeyed. These results are useful in understanding the behavior of tungsten dust generated in nuclear fusion devices as well as for the preparation, formation, and application of tungsten powders.

  4. Surface induced dissociation yields substructure of Methanosarcina thermophila 20S proteasome complexes

    PubMed Central

    Ma, Xin; Loo, Joseph A.; Wysocki, Vicki H.

    2015-01-01

    Native mass spectrometry (MS) and surface induced dissociation (SID) have been applied to study the stoichiometry and quaternary structure of non-covalent protein complexes. In this study, Methanosarcina thermophila 20S proteasome, which consists of four stacked heptameric rings (α7β7β7α7 symmetry), has been selected to explore the SID dissociation pattern of a complicated stacked ring protein complex. SID produces both α and β subunits while collision induced dissociation (CID) produces only highly charged α subunit. In addition, the charge reduced 20S proteasome produces the α7β7 fragment, reflecting the stacked ring topology of the complex. The combination of SID and charge reduction is shown to be a powerful tool for the study of protein complex structure. PMID:26005366

  5. A molecular dynamics study of melting and dissociation of tungsten nanoparticles

    SciTech Connect

    Li, Min; Wang, Jun; Fu, Baoqin; Hou, Qing

    2015-12-15

    Molecular dynamics simulations were conducted to study the melting and dissociation of free tungsten nanoparticles. For the various interatomic potentials applied, the melting points of the tungsten nanoparticles increased with increasing nanoparticle diameter. Combining these results with the melting point of bulk tungsten in the experiment, the melting point of nanoparticles with diameters ranging from 4 to 12 nm could be determined. As the temperature increases, free nanoparticles are subject to dissociation phenomena. The dissociation rate was observed to follow Arrhenius behavior, and the Meyer–Neldel rule was obeyed. These results are useful in understanding the behavior of tungsten dust generated in nuclear fusion devices as well as for the preparation, formation, and application of tungsten powders.

  6. Revealing Dissociative Electron Attachment Dynamics in Polyatomic Molecules Using Momentum Imaging Experiments and Electron Scattering Calculations

    NASA Astrophysics Data System (ADS)

    Belkacem, Ali; Slaughter, Daniel

    2015-05-01

    Understanding electron-driven chemical reactions is important for improving a variety of technological applications such as materials processing and the important role they play in the radiation damage in bulk matter. Furthermore, dissociative electron attachment often exhibits site-selective bond cleavage, which holds promise for prediction and precise control of electron-driven chemical reactions. Recent dynamical studies of these reactions have demonstrated that an understanding of anion dissociation dynamics beyond simple one-dimensional models is crucial in interpreting the measured fragment angular distributions. We combine ion fragment momentum imaging experiments with electron attachment entrance amplitude calculations to interrogate the non-Born-Oppenheimer dynamics of dissociative electron attachment in polyatomic molecules. We will report recent experimental developments in molecules of technological interest including methanol, methane and uracil. Work supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  7. Comparison of vibration dissociation coupling and radiative heat transfer models for AOTV/AFE flowfields

    NASA Technical Reports Server (NTRS)

    Carlson, Leland A.; Bobskill, Glenn J.; Greendyke, Robert B.

    1988-01-01

    A series of detailed studies comparing various vibration dissociation coupling models, reaction systems and rates, and radiative heating models has been conducted for the nonequilibrium stagnation region of an AFE/AOTV vehicle. Atomic and molecular nonequilibrium radiation correction factors have been developed and applied to various absorption coefficient step models, and a modified vibration dissociation coupling model has been shown to yield good vibration/electronic temperature and concentration profiles. While results indicate sensitivity to the choice of vibration dissociation coupling model and to the nitrogen electron impact ionization rate, by proper combinations accurate flowfield and radiative heating results can be obtained. These results indicate that nonequilibrium effects significantly affect the flowfield and the radiative heat transfer. However, additional work is needed in ionization chemistry and absorption coefficient modeling.

  8. What contributes to predicting change in the treatment of dissociation: initial levels of dissociation, PTSD, or overall distress?

    PubMed

    Brand, Bethany L; Stadnik, Ryan

    2013-01-01

    Individuals with dissociative disorders (DDs) suffer from high levels of dissociation as well as posttraumatic stress disorder (PTSD) and general distress. No research has investigated how changes in dissociation relate to changes in other symptoms over the course of treatment in patients with DD. Using a prospective, naturalistic design, we collected reports of symptoms from a sample of therapists and their patients diagnosed with dissociative identity disorder or dissociative disorder not otherwise specified who participated in the Treatment Outcome of Patients with Dissociative Disorders study. The patients completed surveys at intake (Time 1) into the study and at 30-month follow-up (Time 4). We found that dissociative symptoms, including amnesia, depersonalization/derealization, and absorption, at the initial assessment of the study ("initial") were related to initial levels of PTSD and general distress and that changes in dissociative symptoms were related to changes in PTSD and general distress. Initial dissociation was a significant predictor of change in dissociation at 30 months when we controlled for length of time for follow-up, length of time practicing therapy, and length of time treating dissociative patients. Our results suggest that a reduction in dissociative symptoms in DD patients is associated with reductions in the overall severity of dissociative, posttraumatic stress, and distress symptoms. PMID:23627481

  9. Childhood Traumatic Experiences, Dissociative Symptoms, and Dissociative Disorder Comorbidity Among Patients With Panic Disorder: A Preliminary Study.

    PubMed

    Ural, Cenk; Belli, Hasan; Akbudak, Mahir; Tabo, Abdulkadir

    2015-01-01

    This study assessed childhood trauma history, dissociative symptoms, and dissociative disorder comorbidity in patients with panic disorder (PD). A total of 92 psychotropic drug-naive patients with PD, recruited from outpatient clinics in the psychiatry department of a Turkish hospital, were involved in the study. Participants were assessed using the Structured Clinical Interview for DSM-IV Dissociative Disorders (SCID-D), Dissociation Questionnaire, Panic and Agoraphobia Scale, Panic Disorder Severity Scale, and Childhood Trauma Questionnaire. Of the patients with PD, 18 (19%) had a comorbid dissociative disorder diagnosis on screening with the SCID-D. The most prevalent disorders were dissociative disorder not otherwise specified, dissociative amnesia, and depersonalization disorders. Patients with a high degree of dissociation symptoms and dissociative disorder comorbidity had more severe PD than those without (p < .05). All of the childhood trauma subscales used were correlated with the severity of symptoms of dissociation and PD. Among all of the subscales, the strongest relationship was with childhood emotional abuse. Logistic regression analysis showed that emotional abuse and severity of PD were independently associated with dissociative disorder. In our study, a significant proportion of the patients with PD had concurrent diagnoses of dissociative disorder. We conclude that the predominance of PD symptoms at admission should not lead the clinician to overlook the underlying dissociative process and associated traumatic experiences among these patients.

  10. What contributes to predicting change in the treatment of dissociation: initial levels of dissociation, PTSD, or overall distress?

    PubMed

    Brand, Bethany L; Stadnik, Ryan

    2013-01-01

    Individuals with dissociative disorders (DDs) suffer from high levels of dissociation as well as posttraumatic stress disorder (PTSD) and general distress. No research has investigated how changes in dissociation relate to changes in other symptoms over the course of treatment in patients with DD. Using a prospective, naturalistic design, we collected reports of symptoms from a sample of therapists and their patients diagnosed with dissociative identity disorder or dissociative disorder not otherwise specified who participated in the Treatment Outcome of Patients with Dissociative Disorders study. The patients completed surveys at intake (Time 1) into the study and at 30-month follow-up (Time 4). We found that dissociative symptoms, including amnesia, depersonalization/derealization, and absorption, at the initial assessment of the study ("initial") were related to initial levels of PTSD and general distress and that changes in dissociative symptoms were related to changes in PTSD and general distress. Initial dissociation was a significant predictor of change in dissociation at 30 months when we controlled for length of time for follow-up, length of time practicing therapy, and length of time treating dissociative patients. Our results suggest that a reduction in dissociative symptoms in DD patients is associated with reductions in the overall severity of dissociative, posttraumatic stress, and distress symptoms.

  11. Imaging of the dissociation dynamics of polyatomic molecules following low-energy electron resonant attachment

    NASA Astrophysics Data System (ADS)

    Belkacem, Ali

    2014-05-01

    There is a very large body of experimental work on dissociative electron attachment to molecules but the majority of that work is focused on the measurement of absolute total cross sections or energetic positions of the resonances. There is scarce information on the dynamics of electron attachment and the subsequent dissociation that often involves highly non-Born-Oppenheimer dynamics, funneling through conical intersections or intricate nuclear motion during the dissociation process. Through COLTRIMS detection techniques we investigate the electron attachment in a fixed-in-frame manner that yields direct information on the symmetries of the neutral and negatively charged resonant states. We will present a study that combines experimental data along with theoretical analysis of dissociative electron attachment to carbon dioxide, methanol and uracil. In these studies we demonstrated that an understanding of anion dissociation dynamics beyond simple one-dimensional models is crucial in interpreting the measured angular distributions. This work is supported by the Chemical Sciences Biosciences and Geosciences Division, Basic Energy Sciences, DOE.

  12. Conditional dissociation as a punishment mechanism in the evolution of cooperation

    NASA Astrophysics Data System (ADS)

    Qu, Xinglong; Zhou, Changli; Cao, Zhigang; Yang, Xiaoguang

    2016-05-01

    Recent studies show that conditional dissociation, a.k.a. post-interaction partner-refusal, can promote the emergence and stability of cooperation. However, in most of these studies, players' strategies are restricted to pure ones, which is obviously inconsistent with many biological and economic situations. Another concern with line of these studies is that conditional dissociation is often combined with other mechanisms. These mechanisms may favor cooperation per se, leaving it unclear whether conditional dissociation is indeed a key factor. In this paper, we study a clean model, pruning all the factors other than conditional dissociation that may favor cooperation. We find that conditional dissociation, which could be viewed as a variant of peer punishment, does promote cooperation, no matter whether mixed strategies are allowed or not. This confirms the previous findings in the literature. In addition, compared with the pure strategy scenario, cooperators are less competitive when mixed strategies are allowed. Our main finding is supported by both the numerical simulations and the theoretical analysis of Neutrally Stable Strategy. We also find that cooperative behavior is favored when waiting time and/or the population's lifespan are longer.

  13. Predicting Addiction Potential on the Basis of Early Traumatic Events, Dissociative Experiences, and Suicide Ideation

    PubMed Central

    Sajadi, Seyedeh Fatemeh; Hajjari, Zahra; Zargar, Yadollah; Mehrabizade Honarmand, Mahnaz; Arshadi, Nasrin

    2014-01-01

    Background: There is a great deal of medical literature suggesting that substance use disorder is a serious clinical concern, affecting general population and associated with considerable economic, societal, and personal costs. Objectives: This study sought to clarify the relationship between early trauma, dissociative experience, and suicide ideation as predictive factors of active and passive addiction potential (A/PAP) in high-school students. Patients and Methods: Three hundred students with the mean age of 15.72 y were selected via multistage random sampling. All participants were asked to complete Iranian addiction potential scale, early trauma inventory, dissociative experiences scale, and Beck’s suicide ideation scale. Analyzing data was done using canonical correlation. Results: Structural coefficients showed that the pattern of high scores in A/PAP correlates with the pattern of high scores in early trauma, dissociative experience and suicide ideation. The findings of the study showed that the combination of low A/PAP can probably decrease the likelihood of early trauma, dissociative experience and suicide ideation. Conclusions: Early trauma, dissociative experience, and suicide ideation can predict A/PAP and explain the considerable variance of survival index. PMID:25741480

  14. In-Vacuum Dissociator for Atomic-Hydrogen Masers

    NASA Technical Reports Server (NTRS)

    Vessot, R. F.

    1987-01-01

    Thermal control and vacuum sealing achieved while contamination avoided. Simple, relatively inexpensive molecular-hydrogen dissociator for atomic-hydrogen masers used on Earth or in vacuum of space. No air cooling required, and absence of elastomeric O-ring seals prevents contamination. In-vacuum dissociator for atomic hydrogen masers, hydrogen gas in glass dissociator dissociated by radio-frequency signal transmitted from surrounding 3-turn coil. Heat in glass conducted away by contacting metal surfaces.

  15. Evaluation of the maxillary premolar roots dissociation using radiographic holders with conventional and digital radiography.

    PubMed

    Bardauil, Marcia Regina Ramalho da Silva; Moura Netto, Cacio de; Moura, Abílio Albuquerque Maranhão de

    2010-01-01

    This in vivo study evaluated the dissociation quality of maxillary premolar roots combining variations of vertical and horizontal angulations by using X-ray holders (Rinn -XCP), and made a comparison between two types of intraoral radiography systems - conventional film (Kodak Insight, Rochester, USA) and digital radiography (Kodak RVG 6100, Kodak, Rochester, USA). The study sample was comprised of 20 patients with a total of 20 maxillary premolars that were radiographed, using the paralleling angle technique (GP), with a 20º variation of the horizontal angle (GM) and 25º variation of the horizontal angle combined with 15º vertical angle (GMV). Each image was independently analyzed by two experienced examiners. These examiners assigned a score to the diagnostic capability of root dissociation and the measurement of the distance between the apexes. Statistical data was derived using the Wilcoxon Signed Rank test, Friedman and T test. The means of the measured distances between buccal and lingual root apexes were greater for the GMV, which ranged from 2.3 mm to 3.3 mm. A statistically significant difference was found between GM and GMV when compared to GP with p < 0.01. An established best diagnostic dissociation roots image was found in the GMV. These results support the use of the anterior X-ray holders which offer a better combined deviation (GMV) to dissociate maxillary premolar roots in both radiography systems.

  16. Kinetics of Propargyl Radical Dissociation.

    PubMed

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling. PMID:25871530

  17. Kinetics of Propargyl Radical Dissociation.

    PubMed

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling.

  18. Does phasic trauma treatment make patients with dissociative identity disorder treatment more dissociative?

    PubMed

    Brand, Bethany; Loewenstein, Richard J

    2014-01-01

    Proponents of the iatrogenic model of the etiology of dissociative identity disorder (DID) have expressed concern that treatment focused on direct engagement and interaction with dissociated self-states harms DID patients. However, empirical data have shown that this type of DID treatment is beneficial. Analyzing data from the prospective Treatment of Patients With Dissociative Disorders (TOP DD) Study, we test empirically whether DID treatment is associated with clinically adverse manifestations of dissociated self-states: acting so differently that one feels like different people, hearing voices, and dissociative amnesia. We show that, over the course of the study, there were significant decreases in feeling like different people and hearing voices. These results indicate that this form of DID treatment does not lead to symptomatic worsening in these dimensions, as predicted by the iatrogenic model. Indeed, treatment provided by TOP DD therapists reduced, rather than increased, the extent to which patients experienced manifestations of pathological dissociation. Because severe symptomatology and impairment are associated with DID, iatrogenic harm may come from depriving DID patients of treatment that targets DID symptomatology. PMID:24377972

  19. Does phasic trauma treatment make patients with dissociative identity disorder treatment more dissociative?

    PubMed

    Brand, Bethany; Loewenstein, Richard J

    2014-01-01

    Proponents of the iatrogenic model of the etiology of dissociative identity disorder (DID) have expressed concern that treatment focused on direct engagement and interaction with dissociated self-states harms DID patients. However, empirical data have shown that this type of DID treatment is beneficial. Analyzing data from the prospective Treatment of Patients With Dissociative Disorders (TOP DD) Study, we test empirically whether DID treatment is associated with clinically adverse manifestations of dissociated self-states: acting so differently that one feels like different people, hearing voices, and dissociative amnesia. We show that, over the course of the study, there were significant decreases in feeling like different people and hearing voices. These results indicate that this form of DID treatment does not lead to symptomatic worsening in these dimensions, as predicted by the iatrogenic model. Indeed, treatment provided by TOP DD therapists reduced, rather than increased, the extent to which patients experienced manifestations of pathological dissociation. Because severe symptomatology and impairment are associated with DID, iatrogenic harm may come from depriving DID patients of treatment that targets DID symptomatology.

  20. MDMA, cannabis, and cocaine produce acute dissociative symptoms.

    PubMed

    van Heugten-Van der Kloet, Dalena; Giesbrecht, Timo; van Wel, Janelle; Bosker, Wendy M; Kuypers, Kim P C; Theunissen, Eef L; Spronk, Desirée B; Jan Verkes, Robbert; Merckelbach, Harald; Ramaekers, Johannes G

    2015-08-30

    Some drugs of abuse may produce dissociative symptoms, but this aspect has been understudied. We explored the dissociative potential of three recreational drugs (3,4-methylenedioxymethamphetamine (MDMA), cannabis, and cocaine) during intoxication and compared their effects to literature reports of dissociative states in various samples. Two placebo-controlled studies were conducted. In Study 1 (N=16), participants received single doses of 25, 50, and 100 mg of MDMA, and placebo. In Study 2 (N=21), cannabis (THC 300 µg/kg), cocaine (HCl 300 mg), and placebo were administered. Dissociative symptoms as measured with the Clinician-Administered Dissociative States Scale (CADSS) significantly increased under the influence of MDMA and cannabis. To a lesser extent, this was also true for cocaine. Dissociative symptoms following MDMA and cannabis largely exceeded those observed in schizophrenia patients, were comparable with those observed in Special Forces soldiers undergoing survival training, but were lower compared with ketamine-induced dissociation. Cocaine produced dissociative symptoms that were comparable with those observed in schizophrenia patients, but markedly less than those in Special Forces soldiers and ketamine users. Thus, MDMA and cannabis can produce dissociative symptoms that resemble dissociative pathology. The study of drug induced dissociation is important, because it may shed light on the mechanisms involved in dissociative psychopathology.

  1. Cognitive Processes in Dissociation: Comment on Giesbrecht et al. (2008)

    ERIC Educational Resources Information Center

    Bremner, J. Douglas

    2010-01-01

    In their recent review "Cognitive Processes in Dissociation: An Analysis of Core Theoretical Assumptions," published in "Psychological Bulletin", Giesbrecht, Lynn, Lilienfeld, and Merckelbach (2008) have challenged the widely accepted trauma theory of dissociation, which holds that dissociative symptoms are caused by traumatic stress. In doing so,…

  2. MDMA, cannabis, and cocaine produce acute dissociative symptoms.

    PubMed

    van Heugten-Van der Kloet, Dalena; Giesbrecht, Timo; van Wel, Janelle; Bosker, Wendy M; Kuypers, Kim P C; Theunissen, Eef L; Spronk, Desirée B; Jan Verkes, Robbert; Merckelbach, Harald; Ramaekers, Johannes G

    2015-08-30

    Some drugs of abuse may produce dissociative symptoms, but this aspect has been understudied. We explored the dissociative potential of three recreational drugs (3,4-methylenedioxymethamphetamine (MDMA), cannabis, and cocaine) during intoxication and compared their effects to literature reports of dissociative states in various samples. Two placebo-controlled studies were conducted. In Study 1 (N=16), participants received single doses of 25, 50, and 100 mg of MDMA, and placebo. In Study 2 (N=21), cannabis (THC 300 µg/kg), cocaine (HCl 300 mg), and placebo were administered. Dissociative symptoms as measured with the Clinician-Administered Dissociative States Scale (CADSS) significantly increased under the influence of MDMA and cannabis. To a lesser extent, this was also true for cocaine. Dissociative symptoms following MDMA and cannabis largely exceeded those observed in schizophrenia patients, were comparable with those observed in Special Forces soldiers undergoing survival training, but were lower compared with ketamine-induced dissociation. Cocaine produced dissociative symptoms that were comparable with those observed in schizophrenia patients, but markedly less than those in Special Forces soldiers and ketamine users. Thus, MDMA and cannabis can produce dissociative symptoms that resemble dissociative pathology. The study of drug induced dissociation is important, because it may shed light on the mechanisms involved in dissociative psychopathology. PMID:26003508

  3. Cognitive Processes in Dissociation: An Analysis of Core Theoretical Assumptions

    ERIC Educational Resources Information Center

    Giesbrecht, Timo; Lilienfield, Scott O.; Lynn, Steven Jay; Merckelbach, Harald

    2008-01-01

    Dissociation is typically defined as the lack of normal integration of thoughts, feelings, and experiences into consciousness and memory. The present article critically evaluates the research literature on cognitive processes in dissociation. The authors' review indicates that dissociation is characterized by subtle deficits in neuropsychological…

  4. The dissociation energy of N2

    NASA Technical Reports Server (NTRS)

    Almloef, Jan; Deleeuw, Bradley J.; Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Siegbahn, Per

    1989-01-01

    The requirements for very accurate ab initio quantum chemical prediction of dissociation energies are examined using a detailed investigation of the nitrogen molecule. Although agreement with experiment to within 1 kcal/mol is not achieved even with the most elaborate multireference CI (configuration interaction) wave functions and largest basis sets currently feasible, it is possible to obtain agreement to within about 2 kcal/mol, or 1 percent of the dissociation energy. At this level it is necessary to account for core-valence correlation effects and to include up to h-type functions in the basis. The effect of i-type functions, the use of different reference configuration spaces, and basis set superposition error were also investigated. After discussing these results, the remaining sources of error in our best calculations are examined.

  5. The charmonium dissociation in an ''anomalous wind''

    DOE PAGES

    Sadofyev, Andrey V.; Yin, Yi

    2016-01-11

    We study the charmonium dissociation in a strongly coupled chiral plasma in the presence of magnetic field and axial charge imbalance. This type of plasma carries "anomalous flow" induced by the chiral anomaly and exhibits novel transport phenomena such as chiral magnetic effect. We found that the "anomalous flow" would modify the charmonium color screening length by using the gauge/gravity correspondence. We derive an analytical expression quantifying the "anomalous flow" experienced by a charmonium for a large class of chiral plasma with a gravity dual. We elaborate on the similarity and it qualitative difference between anomalous effects on the charmoniummore » color screening length which are model-dependent and those on the heavy quark drag force which are fixed by the second law of thermodynamics. As a result, we speculate on the possible charmonium dissociation induced by the chiral anomaly in heavy ion collisions.« less

  6. Theoretical dissociation energies for ionic molecules

    NASA Technical Reports Server (NTRS)

    Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

    1986-01-01

    Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

  7. Fluid hydrogen at high density - Pressure dissociation

    NASA Technical Reports Server (NTRS)

    Saumon, Didier; Chabrier, Gilles

    1991-01-01

    A model for the Helmholtz free energy of fluid hydrogen at high density and high temperature is developed. This model aims at describing both pressure and temperature dissociation and ionization and bears directly on equations of state of partially ionized plasmas, as encountered in astrophysical situations and high-pressure experiments. This paper focuses on a mixture of hydrogen atoms and molecules and is devoted to the study of the phenomenon of pressure dissociation at finite temperatures. In the present model, the strong interactions are described with realistic potentials and are computed with a modified Weeks-Chandler-Andersen fluid perturbation theory that reproduces Monte Carlo simulations to better than 3 percent. Theoretical Hugoniot curves derived from the model are in excellent agreement with experimental data.

  8. Grammatical category dissociation in multilingual aphasia.

    PubMed

    Faroqi-Shah, Yasmeen; Waked, Arifi N

    2010-03-01

    Word retrieval deficits for specific grammatical categories, such as verbs versus nouns, occur as a consequence of brain damage. Such deficits are informative about the nature of lexical organization in the human brain. This study examined retrieval of grammatical categories across three languages in a trilingual person with aphasia who spoke Arabic, French, and English. In order to delineate the nature of word production difficulty, comprehension was tested, and a variety of concomitant lexical-semantic variables were analysed. The patient demonstrated a consistent noun-verb dissociation in picture naming and narrative speech, with severely impaired production of verbs across all three languages. The cross-linguistically similar noun-verb dissociation, coupled with little evidence of semantic impairment, suggests that (a) the patient has a true "nonsemantic" grammatical category specific deficit, and (b) lexical organization in multilingual speakers shares grammatical class information between languages. The findings of this study contribute to our understanding of the architecture of lexical organization in bilinguals.

  9. Dynamics of Dissociative Electron Attachment to Methane

    NASA Astrophysics Data System (ADS)

    Rescigno, T. N.; Douguet, N.; Fonseca, S.; Orel, A. E.; Slaughter, D. S.; Belkacem, A.

    2015-05-01

    We present the results of a theoretical ad experimental study of dissociative electron attachment (DEA) to CH4. The total DEA cross section is dominated by a single broad peak centered near 10 eV, leading predominantly to H-/CH4 and CH2-/CH4dissociation channels. We will present evidence that both of these ion channels result from excitation of a triply degenerate Feshbach resonance (doubly excited negative ion state) of 2T2 symmetry whose parent is the lowest excited triplet state of the neutral molecule. We will present calculated angular distributions based on analysis of the entrance amplitudes obtained from the results of complex Kohn scattering calculations along with experimentally measured angular distributions obtained using the COLTRIMS method. Work performed under the auspices of the US DOE by the LBNL and supported by the U.S. DOE Office of Basic Energy Sciences, Division of Chemical Sciences.

  10. Vibrational relaxation and dissociation in nitrogen

    NASA Technical Reports Server (NTRS)

    Varghese, Philip L.; Gonzales, David A.

    1991-01-01

    Calculations of the vibrational and dissociation transition probabilities are made for N2-N2 and N2-N collisions by means of a semiclassical N-state approximation. The flaws in previous techniques are reviewed, with special attention given to the prediction of overtones. The method presented ignores the effects of molecular rotation and employs a revised extended Rydberg intermolecular potential to describe diatom-diatom and diatom-atom collisions. The collision velocities investigated exhibit probabilities of less than unity by means of the N-state method. The continuum is quantized to treat dissociation, and the collision results demonstrate probability enhancements for V-V-T transitions in both bound-bound and bound-free transitions. The technique is of particular interest for the theoretical modeling of reentry flows such as those encountered in aerobraking maneuvers.

  11. SCL-90 symptom patterns: indicators of dissociative disorders.

    PubMed

    Steinberg, Marlene; Barry, Declan T; Sholomskas, Diane; Hall, Pamela

    2005-01-01

    The purpose of this study was to examine the SCL-90 profiles of adult outpatients with and without dissociative disorders. A total of 194 participants were administered the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R) and the Symptom Checklist-90 (SCL-90). Patients with dissociative identity disorder (DID) reported significantly higher SCL-90 Global Severity Index (GSI) and individual subscale scores than those without dissociative disorders. It is recommended that patients who are polysymptomatic on the SCL-90 be considered for follow-up dissociative symptom assessment to aid differential diagnosis and to inform subsequent treatment.

  12. Psychogenic or dissociative fugue: a clinical investigation of five cases.

    PubMed

    Coons, P M

    1999-06-01

    Dissociative fugue (formerly psychogenic fugue) is a rare and little understood dissociative disorder. Following a review of the pertinent literature, five cases of dissociative fugue are described. These cases were systematically studied with a comprehensive history, mental status examination, physical and neurological evaluation, review of previous medical and psychiatric records, and psychological testing including MMPI, WAIS-R, electroencephalogram, and Dissociative Experiences Scale. An unexpected finding was that, in some cases, associated criminal activity may allow the person with dissociative fugue to continue to function in spite of their loss of memory and original identity.

  13. Coulomb dissociation of {sup 27} P

    SciTech Connect

    Beceiro, S.; Cortina-Gil, D.; Suemmerer, K.

    2010-04-26

    The {sup 26}Al nucleus has a shorter life-time than the Universe showing that the nucleosynthesis of this element might be an ongoing process in stars. The reaction {sup 26}Si(p,gamma){sup 27} P competes with the production of {sup 26}Al. Coulomb dissociation of {sup 27} P is an indirect method to measure that reaction. An experiment was performed at GSI with a {sup 36}Ar primary beam at 500 MeV to measure this reaction.

  14. The Bond Dissociation Energies of 1-Butene

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    The bond dissociation energies of 1-butene and several calibration systems are computed using the G2(MP2) approach. The agreement between the calibration systems and experiment is very good. The computed values for 1-butene are compared with calibration systems and the agreement between the computed results for 1-butene and the "rule of thumb" values from the smaller systems is remarkably good.

  15. Regional dissociated heterochrony in multivariate analysis.

    PubMed

    Mitteroecker, P; Gunz, P; Weber, G W; Bookstein, F L

    2004-12-01

    Heterochrony, the classic framework to study ontogeny and phylogeny, in essence relies on a univariate concept of shape. Though principal component plots of multivariate shape data seem to resemble classical bivariate allometric plots, the language of heterochrony cannot be translated directly into general multivariate methodology. We simulate idealized multivariate ontogenetic trajectories and demonstrate their behavior in principal component plots in shape space and in size-shape space. The concept of "dissociation", which is conventionally regarded as a change in the relationship between shape change and size change, appears to be algebraically the same as regional dissociation - the variation of apparent heterochrony by region. Only if the trajectories of two related species lie along exactly the same path in shape space can the classic terminology of heterochrony apply so that pure dissociation of size change against shape change can be detected. We demonstrate a geometric morphometric approach to these issues using adult and subadult crania of 48 Pan paniscus and 47 P. troglodytes. On each specimen we digitized 47 landmarks and 144 semilandmarks on ridge curves and the external neurocranial surface. The relation between these two species' growth trajectories is too complex for a simple summary in terms of global heterochrony.

  16. Dynamics of unimolecular dissociation of silylene

    NASA Astrophysics Data System (ADS)

    NoorBatcha, I.; Raff, Lionel M.; Thompson, Donald L.; Viswanathan, R.

    1986-04-01

    The semiempirical valence-bond surface formulated by Viswanathan et al. [J. Phys. Chem. 89, 1428 (1985)] for the unimolecular dissociation of SiH2 has been fitted to an analytical function of the type suggested by Murrell and co-workers [J. Phys. Chem. 88, 4887 (1984)]. The fitted surface accurately represents most of the experimental and CI results. The dynamics of the unimolecular dissociation of SiH2 to form Si and H2 have been investigated by classical trajectory methods on this fitted surface. The effect of describing the initial state of the molecule using normal and local mode approximations has been studied. In spite of the presence of the heavier atom, no bond or mode specificity is observed. The product energy distribution is found to be statistical. Using the RRK model, the high-pressure limiting rate coefficient is found to be k(T,∞)=3.38×1012 exp[-61.6 kcal mol-1/RT] s-1, which is less than the dissociation rate for SiH4. This has been attributed to the higher activation energy for SiH2 and to a statistical factor.

  17. Mechanistic studies of multipole storage assisted dissociation.

    PubMed

    Håkansson, K; Axelsson, J; Palmblad, M; Håkansson, P

    2000-03-01

    The degree and onset of fragmentation in multipole storage assisted dissociation (MSAD) have been investigated as functions of several hexapole parameters. Strict studies of hexapole charge density (number of ions injected) and hexapole storage time were made possible by placing a pulsed shutter in front of the entrance to the mass spectrometer. The results obtained show that the charge density is the most critical parameter, but also dependencies on storage time, radio-frequency (rf) -amplitude, and pressure are seen. From these data, and from simulations of the ion trajectories inside the hexapole, a mechanism for MSAD, similar to the ones for sustained off-resonance irradiation (SORI), and for low energy collisionally induced dissociation in the collision multipole of a triple quadrupole mass spectrometer, is proposed. It is believed that, at higher charge densities, ions are pushed to larger hexapole radii where the electric potential created by the rf field is higher, forcing the ions to oscillate radially to higher amplitudes and thereby reach higher (but still relatively low) kinetic energies. Multiple collisions with residual gas molecules at these elevated energies then heat up the molecules to their dissociation threshold. Further support for this mechanism is obtained from a comparison of MSAD and SORI spectra which are almost identical in appearance.

  18. Gas Hydrate Dissociation in the Ocean

    NASA Astrophysics Data System (ADS)

    Conroy, Devin; Smith, Stefan Llewellyn

    2006-11-01

    Methane gas is known to exist in extremely large quantities below the sea floor in the sediment of the deep and cold oceanic and in permafrost regions. Due to the large hydrostatic pressure and cool temperatures the gas reacts with the surrounding water to form a crystalline substance known as a gas hydrate. The fate of these reserves is very important to climate on earth because methane is a much more efficient greenhouse gas then carbon dioxide. The dissociation process in general can occur by either a decrease in pressure or an increase in temperature. In this study we concentrate on the latter. Once the hydrate dissociates, water and free gas remain above the phase boundary, occupying a larger volume than the original solid, and are be transported through the sediment. We have modeled this physical mechanism using volume averaged equations in a porous medium with a coupled two-phase flow. The movement of the phase boundary, which is proportional to the rate of heat transfer to this interface, is modeled as a Stefan type melting problem. The resultant governing equations are solved numerically, using a front fixing method to fix the phase boundary, to determine the rate of gas flux through the sediment and the dissociation rate.

  19. Dissociative recombination of N2H+

    NASA Astrophysics Data System (ADS)

    dos Santos, S. Fonseca; Ngassam, V.; Orel, A. E.; Larson, Å.

    2016-08-01

    The direct and indirect mechanisms of dissociative recombination of N2H+ are theoretically studied. At low energies, the electron capture is found to be driven by recombination into bound Rydberg states, while at collision energies above 0.1 eV, the direct capture and dissociation along electronic resonant states becomes important. Electron-scattering calculations using the complex Kohn variational method are performed to obtain the scattering matrix as well as energy positions and autoionization widths of resonant states. Potential-energy surfaces of electronic bound states of N2H and N2H+ are computed using structure calculations with the multireference configuration interaction method. The cross section for the indirect mechanism is calculated using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Here vibrational excitations of the ionic core from v =0 to v =1 and v =2 for all three normal modes are considered and autoionization is neglected. The cross section for the direct dissociation along electronic resonant states is computed with wave-packet calculations using the multiconfiguration time-dependent Hartree method, where all three internal degrees of freedom are considered. The calculated cross sections are compared to measurements.

  20. Memory repression: brain mechanisms underlying dissociative amnesia.

    PubMed

    Kikuchi, Hirokazu; Fujii, Toshikatsu; Abe, Nobuhito; Suzuki, Maki; Takagi, Masahito; Mugikura, Shunji; Takahashi, Shoki; Mori, Etsuro

    2010-03-01

    Dissociative amnesia usually follows a stressful event and cannot be attributable to explicit brain damage. It is thought to reflect a reversible deficit in memory retrieval probably due to memory repression. However, the neural mechanisms underlying this condition are not clear. We used fMRI to investigate neural activity associated with memory retrieval in two patients with dissociative amnesia. For each patient, three categories of face photographs and three categories of people's names corresponding to the photographs were prepared: those of "recognizable" high school friends who were acquainted with and recognizable to the patients, those of "unrecognizable" colleagues who were actually acquainted with but unrecognizable to the patients due to their memory impairments, and "control" distracters who were unacquainted with the patients. During fMRI, the patients were visually presented with these stimuli and asked to indicate whether they were personally acquainted with them. In the comparison of the unrecognizable condition with the recognizable condition, we found increased activity in the pFC and decreased activity in the hippocampus in both patients. After treatment for retrograde amnesia, the altered pattern of brain activation disappeared in one patient whose retrograde memories were recovered, whereas it remained unchanged in the other patient whose retrograde memories were not recovered. Our findings provide direct evidence that memory repression in dissociative amnesia is associated with an altered pattern of neural activity, and they suggest the possibility that the pFC has an important role in inhibiting the activity of the hippocampus in memory repression.

  1. Prevalence of dissociative disorders among women in the general population.

    PubMed

    Sar, Vedat; Akyüz, Gamze; Doğan, Orhan

    2007-01-15

    This study sought to determine the prevalence of dissociative disorders among women in the general population, as assessed in a representative sample of a city in central Turkey. The Dissociative Disorders Interview Schedule (DDIS), the Borderline Personality Disorder section of the Structured Clinical Interview for DSM-III-R Personality Disorders (SCID-II), and the PTSD-Module of the Structured Clinical Interview for DSM-III-R (SCID) were administered to 628 women in 500 homes. The mean age of participants was 34.8 (S.D.=11.5, range: 18-65); 18.3% of participants (n=115) had a lifetime diagnosis of a dissociative disorder. Dissociative disorder not otherwise specified (DDNOS) was the most prevalent diagnosis (8.3%); 1.1% of the population was diagnosed as having dissociative identity disorder (DID). Participants with a dissociative disorder had borderline personality disorder, somatization disorder, major depression, PTSD, and history of suicide attempt more frequently than did participants without a dissociative disorder. Childhood sexual abuse, physical neglect, and emotional abuse were significant predictors of a dissociative disorder diagnosis. Only 28.7% of the dissociative participants had received psychiatric treatment previously. Because dissociative disorders are trauma-related, significant part of the adult clinical consequences of childhood trauma remains obscure in the minds of mental health professionals and of the overall community. Revisions in diagnostic criteria of dissociative disorders in the DSM-IV are recommended.

  2. Dissociative disorders among Chinese inpatients diagnosed with schizophrenia.

    PubMed

    Yu, Junhan; Ross, Colin A; Keyes, Benjamin B; Li, Ying; Dai, Yunfei; Zhang, Tianhong; Wang, Lanlan; Fan, Qing; Xiao, Zeping

    2010-01-01

    The purpose of this study was to assess the prevalence of dissociative disorders in a sample of Chinese psychiatric inpatients. Participants in the study were 569 consecutively admitted inpatients at Shanghai Mental Health Center, China, of whom 84.9% had a clinical diagnosis of schizophrenia based on the Chinese Classification and Diagnostic Criteria of Mental Disorders, Version 3. All participants completed a self-report measure of dissociation (the Dissociative Experiences Scale), and none had a prior diagnosis of a dissociative disorder. A total of 96 randomly selected participants were interviewed with a structured interview (the Dissociative Disorders Interview Schedule) and a clinical interview. These 96 patients did not differ significantly from the 473 patients who were not interviewed on any demographic measures or who did not complete the self-report dissociation measure. A total of 28 patients (15.3%, after weighting of the data) received a clinical diagnosis of a dissociative disorder based on Diagnostic and Statistical Manual of Mental Disorders (4th ed., text rev.) criteria. Dissociative identity disorder was diagnosed in 2 patients (0.53%, after weighting). Compared to the patients without a dissociative disorder, patients with dissociative disorders were significantly more likely to report childhood abuse (57.1% vs. 22.1%), but the 2 groups did not differ significantly on any demographic measures. Dissociative disorders were readily identified in an inpatient psychiatric population in China.

  3. Cognitive Processes in Dissociation: Comment on Giesbrecht et al. (2008)

    PubMed Central

    Bremner, J. Douglas

    2010-01-01

    In “Cognitive Processes in Dissociation: An Analysis of Core Theoretical Assumptions,” published in Psychological Bulletin, Giesbrecht, Lynn, Lilienfeld, and Merckelbach (2008) have challenged the widely accepted trauma theory of dissociation, which holds that dissociative symptoms are caused by traumatic stress. In doing so the authors outline a series of links between various constructs, such as fantasy proneness, cognitive failures, absorption, suggestibility, altered information-processing, dissociation, and amnesia, claiming that these linkages lead to the false conclusion that trauma causes dissociation. A review of the literature, however, shows that these are not necessarily related constructs. Careful examination of their arguments reveals no basis for the conclusion that there is no association between trauma and dissociation. The current comment offers a critical review and rebuttal of the argument of Giesbrecht et al. that there is no relationship between trauma and dissociation. PMID:20063920

  4. The dissociation constant of water at extreme conditions

    NASA Astrophysics Data System (ADS)

    Gonzalez-Vazquez, Otto; Giacomazzi, Luigi; Pinilla, C.; Scandolo, Sandro

    2013-06-01

    Only one out of 107 water molecules is dissociated in liquid water at ambient conditions, but the concentration of dissociated molecules increases with pressure ad temperature, and water eventually reaches a fully dissociated state when pressure exceeds 50-100 GPa and temperature reaches a few thousand Kelvin. The behavior of the dissociation constant of water (pKa) at conditions intermediate between ambient and the fully dissociated state is poorly known. Yet, the water pKa is a parameter of primary importance in the aqueous geochemistry as it controls the solubility of ions in geological fluids. We present results of molecular dynamics calculations of the pKa water at extreme conditions. Free-energy differences between the undissociated and the dissociated state are calculated by thermodynamic integration along the dissociation path. The calculations are based on a recently developed all-atom polarizable force-field for water, parametrized on density-functional theory calculations.

  5. Childhood sexual abuse, dissociation, and adult self-destructive behavior.

    PubMed

    Rodriguez-Srednicki, O

    2001-01-01

    Female college students reporting a history of childhood sexual abuse (N=175) and not reporting a history of childhood sexual abuse (N=260) were compared on indices of six self-destructive behaviors, including drug use, alcohol abuse, binge eating, self-mutilation, risky sex, and suicidality. The samples were also compared on two measures of dissociation, the Trauma Symptom Checklist dissociation subscale and the Dissociative Experiences Scale. The CSA group had significantly higher mean scores on all the indices of self-destructive behavior except self-mutilation (where the mean difference approached significance), and on both measures of dissociation. One or both dissociation measures were related significantly to each index of self-destructive behavior except binge eating. Multiple regression mediation analyses provided support for the hypothesis that dissociation mediates the relationships between CSA and both drug use and alcohol abuse. Dissociation also explained significant variability when added to the regressions of risky sex and suicidality on CSA.

  6. Malingering dissociative identity disorder: objective and projective assessment.

    PubMed

    Labott, Susan M; Wallach, Heather R

    2002-04-01

    Verification of dissociative identity disorder presents challenges given the complex nature of the illness. This study addressed the concern that this disorder can be successfully malingered on objective and projective psychological tests. 50 undergraduate women were assigned to a Malingering or a Control condition, then completed the Rorschach Inkblot Test and the Dissociative Experiences Scale II. The Malingering group were asked to simulate dissociative identity disorder; controls received instructions to answer all materials honestly. Analysis indicated that malingerers were significantly more likely to endorse dissociative experiences on the Dissociative Experiences Scale II in the range common to patients with diagnosed dissociative identity disorder. However, on the Rorschach there were no significant differences between the two groups. Results suggest that the assessment of dissociative identity disorder requires a multifaceted approach with both objective and projective assessment tools. Research is needed to assess these issues in clinical populations.

  7. The older female patient with a complex chronic dissociative disorder.

    PubMed

    Kluft, Richard P

    2007-01-01

    Dissociative disorders are rarely considered in the diagnostic assessment of older women, despite the fact that the existence, appearance and characteristics of certain dissociative disorders in older populations has been known and described since the 1980s. This communication reviews the core phenomena of Dissociative Identity Disorder and related forms of Dissociative Disorder Not Otherwise Specified, the natural history of their phenomena from youth to old age, and describes common presentations of Dissociative Disorders in older women. It also reviews the treatment of complex chronic dissociative disorders and discusses alternative approaches to their psychotherapy in the older female patient. It is crucial to recognize and respect the importance of appreciating individual differences among older dissociative patients and to individualize their treatments accordingly.

  8. Different types of "dissociation" have different psychological mechanisms.

    PubMed

    Brown, Richard J

    2006-01-01

    The term "dissociation" has been used to describe a wide range of psychological and psychiatric phenomena. The popular conception of dissociation describes it as a unitary phenomenon, with only quantitative differences in severity between the various dissociative conditions. More recently, it has been argued that the available evidence is more consistent with a model that identifies at least two distinct categories of dissociative phenomena-"detachment" and "compartmentalization"- that have different definitions, mechanisms and treatment implications (Holmes, Brown, Mansell, Fearon, Hunter, Frasquilho & Oakley 2005). This paper presents evidence for this bipartite model of dissociation, followed by definitions and descriptions of detachment and compartmentalization. Possible psychological mechanisms underlying these phenomena are then discussed, with particular emphasis on the nature of compartmentalization in conversion disorder, hypnosis, dissociative amnesia and dissociative identity disorder.

  9. Charged Diblock Copolymers at Interfaces: Micelle Dissociation Upon Compression

    SciTech Connect

    Checco, A.; Theodoly, O.; Muller, P.

    2010-05-20

    We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are 'frozen'. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters. keywords - soft matter, liquids and polymers, biological physics, chemical physics and physical chemistry.

  10. Charged Diblock Copolymers at Interfaces: Micelle Dissociation Upon Compression

    SciTech Connect

    Theodoly, O.; Checco, A; Muller, P

    2010-01-01

    We use grazing incidence X-ray scattering to study the surface micellization of charged amphiphilic diblock copolymers poly(styrene-block-acrylic acid) at the air-water interface. Scattering interference peaks are consistent with the formation of hexagonally packed micelles. The remarkable increase of inter-micelle distance upon compression is explained by a dissociation of micelles into a brush. Hence, surface micelles reorganize, whereas micelles of the same copolymers in solutions are 'frozen'. We show indeed that the energetic cost of unimer extraction from micelles is much lower for surface than for solution. Finally, a model combining electrostatic interactions and micelle/brush equilibrium explains surface pressure vs. area without free parameters.

  11. Snapshots In The History Of Dissociative Major Mergers

    NASA Astrophysics Data System (ADS)

    Pacaud, Florian

    2013-10-01

    We propose joint Chandra/HST observations of two z=0.3 cluster mergers presenting offsets between the gas and dark matter distribution. Both were discovered within the follow-up program of the APEX-SZ experiment. The first one shows a bullet structure with a probable bow shock. The new data will permit an accurate joint X-ray, Sunyaev-Zel'dovich effect and lensing analysis to characterize both the thermodynamical state of its intracluster gas and the distribution of dark matter around it. The second cluster lacks good X-ray data and we request a short Chandra observations to confirm the gas distribution. Combined with three similar systems from the APEX-SZ sample, we aim at reconstructing obsevationally the time sequence of dissociative mergers.

  12. Snapshots in the History of Dissociative Major Mergers

    NASA Astrophysics Data System (ADS)

    Pacaud, Florian

    2013-09-01

    We propose joint Chandra/HST observations of two z=0.3 cluster mergers presenting offsets between the gas and dark matter distribution. Both were discovered within the follow-up program of the APEX-SZ experiment. The first one shows a bullet structure with a probable bow shock. The new data will permit an accurate joint X-ray, Sunyaev-Zel'dovich effect and lensing analysis to characterize both the thermodynamical state of its intracluster gas and the distribution of dark matter around it. The second cluster lacks good X-ray data and we request a short Chandra observations to confirm the gas distribution. Combined with three similar systems from the APEX-SZ sample, we aim at reconstructing obsevationally the time sequence of dissociative mergers.

  13. [Questionnaire on dissociative symptoms. German adaptation, reliability and validity of the American Dissociative Experience Scale (DES)].

    PubMed

    Freyberger, H J; Spitzer, C; Stieglitz, R D; Kuhn, G; Magdeburg, N; Bernstein-Carlson, E

    1998-06-01

    The "Fragebogen zu dissoziativen Symptomen (FDS)" represents the authorised German translation and adaptation of the "Dissociative Experience Scale" (DES; Bernstein and Putnam 1986). The original scale comprises 28 items covering dissociative experiences with regard to memory, identity, awareness and cognition according to DSM-III-R and DSM-IV. For the German version, 16 items were added to cover dissociative phenomena according to ICD-10, mainly pseudoneurological conversion symptoms. Reliability and validity of the German version were studied in a total sample of 813 persons and were compared to the results of the original version. Test-retest reliability of the FDS was rtt = 0.88 and Cronbach's consistency coefficient was alpha = 0.93, which is comparable to the results of the DES. The instrument differentiates between different samples (healthy control subjects, students, unselected neurological and psychiatric inpatients, neurological and psychiatric patients with a dissociative disorder and schizophrenics). The FDS is an easily applicable, reliable and valid measure to quantify dissociative experiences.

  14. Mechanisms and energetics of hydride dissociation reactions on surfaces of plasma-deposited silicon thin films

    NASA Astrophysics Data System (ADS)

    Singh, Tejinder; Valipa, Mayur S.; Mountziaris, T. J.; Maroudas, Dimitrios

    2007-11-01

    We report results from a detailed analysis of the fundamental silicon hydride dissociation processes on silicon surfaces and discuss their implications for the surface chemical composition of plasma-deposited hydrogenated amorphous silicon (a-Si:H) thin films. The analysis is based on a synergistic combination of first-principles density functional theory (DFT) calculations of hydride dissociation on the hydrogen-terminated Si(001)-(2×1) surface and molecular-dynamics (MD) simulations of adsorbed SiH3 radical precursor dissociation on surfaces of MD-grown a-Si :H films. Our DFT calculations reveal that, in the presence of fivefold coordinated surface Si atoms, surface trihydride species dissociate sequentially to form surface dihydrides and surface monohydrides via thermally activated pathways with reaction barriers of 0.40-0.55eV. The presence of dangling bonds (DBs) results in lowering the activation barrier for hydride dissociation to 0.15-0.20eV, but such DB-mediated reactions are infrequent. Our MD simulations on a-Si :H film growth surfaces indicate that surface hydride dissociation reactions are predominantly mediated by fivefold coordinated surface Si atoms, with resulting activation barriers of 0.35-0.50eV. The results are consistent with experimental measurements of a-Si :H film surface composition using in situ attenuated total reflection Fourier transform infrared spectroscopy, which indicate that the a-Si :H surface is predominantly covered with the higher hydrides at low temperatures, while the surface monohydride, SiH(s ), becomes increasingly more dominant as the temperature is increased.

  15. Dissociation and memory fragmentation in post-traumatic stress disorder: an evaluation of the dissociative encoding hypothesis.

    PubMed

    Bedard-Gilligan, Michele; Zoellner, Lori A

    2012-01-01

    Several prominent theories of post-traumatic stress disorder (PTSD) posit that peritraumatic dissociation results in insufficient encoding of the trauma memory and that persistent dissociation prevents memory elaboration, resulting in memory fragmentation and PTSD. In this review we summarise the empirical literature on peritraumatic and trait dissociation and trauma narrative fragmentation as measured by meta-memory and rater/objective coding. Across 16 studies to date, the association between dissociation and fragmentation was most prominent when examining peritraumatic dissociation and patient's own ratings of memory fragmentation. This relationship did not hold when examining trait dissociation or rater-coded or computer-generated measures of fragmentation. Thus initial evidence points more towards a strong self-reported association between constructs that is not supported on more objective fragmentation coding. Measurement overlap, construct ambiguity, and exclusion of potential confounds may underlie lack of a strong association between dissociation and objective-rated fragmentation.

  16. The role of water in gas hydrate dissociation

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.

    2004-01-01

    When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

  17. Different urea stoichiometries between the dissociation and denaturation of tobacco mosaic virus as probed by hydrostatic pressure.

    PubMed

    Santos, Jose L R; Aparicio, Ricardo; Joekes, Inés; Silva, Jerson L; Bispo, Jose A C; Bonafe, Carlos F S

    2008-05-01

    Viruses are very efficient self-assembly structures, but little is understood about the thermodynamics governing their directed assembly. At higher levels of pressure or when pressure is combined with urea, denaturation occurs. For a better understanding of such processes, we investigated the apparent thermodynamic parameters of dissociation and denaturation by assuming a steady-state condition. These processes can be measured considering the decrease of light scattering of a viral solution due to the dissociation process, and the red shift of the fluorescence emission spectra, that occurs with the denaturation process. We determined the apparent urea stoichiometry considering the equilibrium reaction of TMV dissociation and subunit denaturation, which furnished, respectively, 1.53 and 11.1 mol of urea/mol of TMV subunit. The denaturation and dissociation conditions were arrived in a near reversible pathway, allowing the determination of thermodynamic parameters. Gel filtration HPLC, electron microscopy and circular dichroism confirmed the dissociation and denaturation processes. Based on spectroscopic results from earlier papers, the calculation of the apparent urea stoichiometry of dissociation and denaturation of several other viruses resulted in similar values, suggesting a similar virus-urea interaction among these systems. PMID:18367310

  18. Different urea stoichiometries between the dissociation and denaturation of tobacco mosaic virus as probed by hydrostatic pressure.

    PubMed

    Santos, Jose L R; Aparicio, Ricardo; Joekes, Inés; Silva, Jerson L; Bispo, Jose A C; Bonafe, Carlos F S

    2008-05-01

    Viruses are very efficient self-assembly structures, but little is understood about the thermodynamics governing their directed assembly. At higher levels of pressure or when pressure is combined with urea, denaturation occurs. For a better understanding of such processes, we investigated the apparent thermodynamic parameters of dissociation and denaturation by assuming a steady-state condition. These processes can be measured considering the decrease of light scattering of a viral solution due to the dissociation process, and the red shift of the fluorescence emission spectra, that occurs with the denaturation process. We determined the apparent urea stoichiometry considering the equilibrium reaction of TMV dissociation and subunit denaturation, which furnished, respectively, 1.53 and 11.1 mol of urea/mol of TMV subunit. The denaturation and dissociation conditions were arrived in a near reversible pathway, allowing the determination of thermodynamic parameters. Gel filtration HPLC, electron microscopy and circular dichroism confirmed the dissociation and denaturation processes. Based on spectroscopic results from earlier papers, the calculation of the apparent urea stoichiometry of dissociation and denaturation of several other viruses resulted in similar values, suggesting a similar virus-urea interaction among these systems.

  19. Collision-induced dissociation of fluoropyridinide anions

    NASA Astrophysics Data System (ADS)

    Kato, Shuji; Lineberger, W. Carl; Bierbaum, Veronica M.

    2007-10-01

    Collision-induced dissociation of ortho-fluoro, meta-fluoro, and 2,6-difluoropyridinide anions are studied using the selected ion flow tube technique. Structures and energetics of the reactants, transition states, and products are calculated at the MP4(SDQ)/6-31 + G(d) level of theory based on the B3LYP/6-311++G(d,p) and/or MP2/6-31 + G(d) optimized geometries. The monofluoropyridinide anions (C5NH3F-) dissociate almost exclusively via loss of an HF molecule, i.e., C5NH2- + HF at low collision energies, in addition to loss of F- at higher energies. 2,6-Difluoropyridinide anions (C5NH2F2-) dissociate via successive loss of HF molecules to form C5NHF- then C5N- depending on the collision energy. The CID results strongly suggest formation of ring-intact pyridynide structures (C5NH2-, C5NHF-) with a bent triple bond embedded in the azine ring systems. Calculated reaction energy diagrams are totally consistent with the experimental observations. Didehydropyridynides C5NH2- and C5NHF- have substantial barriers to decomposition. Tetradehydropyridynide C5N- is a highly strained ring system and metastable with a predicted barrier of about 5 kcal mol-1 (20 kJ mol-1) toward ring-opening to a linear NCCCCC- structure. The observed C5N- species is most likely the linear anion under experimental conditions; however, the ring-intact C5N- pyridynide is a highly energetic species releasing about 80 kcal mol-1 (340 kJ mol-1) of energy upon the ring-opening.

  20. Spin–orbit interaction mediated molecular dissociation

    SciTech Connect

    Kokkonen, E. Jänkälä, K.; Kettunen, J. A.; Heinäsmäki, S.; Karpenko, A.; Huttula, M.; Löytynoja, T.

    2014-05-14

    The effect of the spin–orbit interaction to photofragmentation is investigated in the mercury(II) bromide (HgBr{sub 2}) molecule. Changes in the fragmentation between the two spin–orbit components of Hg 5d photoionization, as well as within the molecular-field-splitted levels of these components are observed. Dissociation subsequent to photoionization is studied with synchrotron radiation and photoelectron-photoion coincidence spectroscopy. The experimental results are accompanied by relativistic ab initio analysis of the photoelectron spectrum.

  1. On the dissociation energy of Mg2

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Mclean, A. D.; Liu, Bowen

    1990-01-01

    The bonding in the X 1Sigma(+)g state of Mg2 is investigated using near-complete valence one-particle Slater and Gaussian basis sets containing up to h functions. It is shown that the four-electron complete CI limit can be approached using a sequence of either second-order CI (SOCI) or interacting correlated fragment (ICF) calculations. At the valence level, the best estimate of the dissociation energy D(e) was 464/cm. This is a lower limit and is probably within 5/cm of the complete basis value.

  2. Ritual homicide during dissociative trance disorder.

    PubMed

    Ferracuti, Stefano; DeMarco, Maria Civita

    2004-02-01

    A case report is described of a man who developed a single period of recurrent episodes of dissociative trance disorder (DTD) during a family stress. The cultural environment was permeated by thoughts and beliefs in magic. During one trance state, the man performed an exorcism on the 6-month-old baby of his brother-in-law, and the baby died from cerebral hemorrhage. In the 5-year follow-up, no other episodes of DTD developed, and the man is serving an 18-year sentence.

  3. Dissociative Ionization of Aromatic and Heterocyclic Molecules

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.

    2003-01-01

    Space radiation poses a major health hazard to humans in space flight. The high-energy charged particles in space radiation ranging from protons to high atomic number, high-energy (HZE) particles, and the secondary species they produce, attack DNA, cells, and tissues. Of the potential hazards, long-term health effects such as carcinogenesis are likely linked to the DNA lesions caused by secondary electrons in the 1 - 30 eV range. Dissociative ionization (DI) is one of the electron collision processes that can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. To understand this process, we have developed a theoretical model for DI. Our model makes use of the fact that electron motion is much faster than nuclear motion and assumes DI proceeds through a two-step process. The first step is electron-impact ionization resulting in a particular state of the molecular ion in the geometry of the neutral molecule. In the second step the ion undergoes unimolecular dissociation. Thus the DI cross section sigma(sup DI)(sub a) for channel a is given by sigma(sup DI)(sub a) = sigma(sup I)(sub a) P(sub D) with sigma(sup I)(sub a) the ionization cross section of channel a and P(sub D) the dissociation probability. This model has been applied to study the DI of H2O, NH3, and CH4, with results in good agreement with experiment. The ionization cross section sigma(sup I)(sub a) was calculated using the improved binary encounter-dipole model and the unimolecular dissociation probability P(sub D) obtained by following the minimum energy path determined by the gradients and Hessians of the electronic energy with respect to the nuclear coordinates of the ion. This model is used to study the DI from the low-lying channels of benzene and pyridine to understand the different product formation in aromatic and heterocyclic molecules. DI study of the DNA base thymine is underway. Solvent effects will also be discussed.

  4. A woman with dermatitis and dissociative periods.

    PubMed

    Wise, T N; Reading, A J

    1975-01-01

    A nineteen year old female with pustular eczema and dissociative spells is presented. The patient has a three year history of severe dermatitis beginning shortly after her marriage. Central dynamic issues appear to be difficulty separating from her mother and an ambivalent identification with a hostile father. The patient also describes fugue-like episodes which occur with emerging aggressive feelings. Psychological testing supported these hypotheses. The relevant literature describing the correlation between aggression and skin disease is reviewed. A final uniform formulation was tentatively proposed that this patient, in addition to a strong genetic component for atopic dermatitis, had her illness abetted by inability to cope with aggressive affects.

  5. Strain-induced water dissociation on supported ultrathin oxide films

    PubMed Central

    Song, Zhenjun; Fan, Jing; Xu, Hu

    2016-01-01

    Controlling the dissociation of single water molecule on an insulating surface plays a crucial role in many catalytic reactions. In this work, we have identified the enhanced chemical reactivity of ultrathin MgO(100) films deposited on Mo(100) substrate that causes water dissociation. We reveal that the ability to split water on insulating surface closely depends on the lattice mismatch between ultrathin films and the underlying substrate, and substrate-induced in-plane tensile strain dramatically results in water dissociation on MgO(100). Three dissociative adsorption configurations of water with lower energy are predicted, and the structural transition going from molecular form to dissociative form is almost barrierless. Our results provide an effective avenue to achieve water dissociation at the single-molecule level and shed light on how to tune the chemical reactions of insulating surfaces by choosing the suitable substrates. PMID:26953105

  6. The responses of dissociative patients on the thematic apperception test.

    PubMed

    Pica, M; Beere, D; Lovinger, S; Dush, D

    2001-07-01

    This study compared the responses of dissociative inpatients and general inpatient psychiatric controls on the Thematic Apperception Test (TAT; Murray, 1943). We found the stories of dissociative participants to be characterized by a greater interpersonal distance and more trauma and dissociation responses than those of the controls. No significant differences were found regarding total number of emotional references, although references to positive emotions were almost nonexistent for the dissociative group. A post hoc analysis of the data found the testing behaviors of dissociative participants to be characterized by switching, trance states, intrainterview amnesias, and affectively loaded card rejections. Questions were raised regarding the relevancy of the findings to clinical practice and how they might explain some of the controversies surrounding the diagnosis of dissociative identity disorder (DID).

  7. Dissociative detachment relates to psychotic symptoms and personality decompensation.

    PubMed

    Allen, J G; Coyne, L; Console, D A

    1997-01-01

    Previous studies have addressed the prominence of psychotic symptoms in conjunction with multiple personality disorder (now dissociative identity disorder). The present study examines the relation between psychotic symptoms and a more pervasive form of dissociative disturbance, namely dissociative detachment. Two hundred sixty-six women in inpatient treatment for severe trauma-related disorders completed the Dissociative Experiences Scale (DES), and 102 of these patients also completed the Millon Clinical Multiaxial Inventory (MCMI-III). A factor analysis of the DES yielded two dimensions of dissociative detachment: detachment from one's own actions and detachment from the self and the environment. Each of these DES dimensions relates strongly to the thought disorder and schizotypal personality disorder scales of the MCMI-III. We propose that severe dissociative detachment, by virtue of loosening the moorings in inner and outer reality, is conducive to psychotic symptoms and personality decompensation.

  8. Multipole storage assisted dissociation, a novel in-source dissociation technique for electrospray ionization generated ions.

    PubMed

    Sannes-Lowery, K; Griffey, R H; Kruppa, G H; Speir, J P; Hofstadler, S A

    1998-01-01

    In this work we present a novel in-source dissociation scheme referred to as multipole storage assisted dissociation (MSAD) for electrospray ionization (ESI) generated ions in which dissociation is effected by employing extended ion accumulation intervals in a high pressure rf-only hexapole assembly prior to mass analysis. Following an extended ion accumulation interval in which ions are confined in the rf-only hexapole, ions are gated out of the hexapole, trapped, and mass analyzed in the trapped ion cell of a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. The accumulation region is comprised of an rf-only hexapole ion guide which separates two electrodes, a biased skimmer cone, and an auxiliary 'gate' electrode at the low pressure end of the hexapole. This technique should be applicable to other mass spectrometry platforms compatible with pulsed ionization sources including quadrupole ion traps, and time-of-flight mass analyzers. This concept is demonstrated with the dissociation of a small protein in which selective fragmentation is observed at labile amino acid linkages producing primarily y-type fragment ions.

  9. Ictal symptoms of anxiety, avoidance behaviour, and dissociation in patients with dissociative seizures

    PubMed Central

    Goldstein, L H; Mellers, J D C

    2006-01-01

    Objective To examine anxiety related seizure symptoms and avoidance behaviour in adults with dissociative (psychogenic non‐epileptic) seizures (DS) in comparison with a group suffering from partial epilepsy. Methods 25 DS and 19 epilepsy patients completed an attack symptom measure, the hospital anxiety and depression scale, the dissociative experiences scale, and the fear questionnaire. Results DS patients reported the presence of significantly greater numbers of somatic symptoms of anxiety during their attacks than the epilepsy group, despite not reporting subjectively higher levels of anxiety. The DS patients also reported higher levels of agoraphobic‐type avoidance behaviour than the epilepsy group. Measures of dissociation were higher in the DS group, who also reported greater symptoms of depression. Conclusions The findings support a model whereby DS occur as a paroxysmal, dissociative response to heightened arousal in the absence of raised general anxiety levels. The model has practical implications for clinical assessment and treatment: in clinical practice, inquiry about these symptoms may help in the diagnosis of DS; with respect to treatment, the anxiety related symptoms and avoidance behaviour prevalent in DS are a potential focus for a cognitive behavioural approach analogous to that used in the treatment of other anxiety disorders. PMID:16614021

  10. The molecular dynamics of adsorption and dissociation of O{sub 2} on Pt(553)

    SciTech Connect

    Jacobse, Leon Dunnen, Angela den; Juurlink, Ludo B. F.

    2015-07-07

    Molecular adsorption and dissociation of O{sub 2} on the stepped Pt(553) surface have been investigated using supersonic molecular beam techniques and temperature programmed desorption. The initial and coverage-dependent sticking probability was determined with the King and Wells technique for various combinations of incident kinetic energy, surface temperature, incident angle, and surface coverage. A comparison with similar data for Pt(533) and Pt(110)(1 × 2) shows quantitatively the same high step-induced sticking at low incident energies compared to Pt(111). The enhancement is therefore insensitive to the exact arrangement of atoms forming surface corrugation. We consider energy transfer and electronic effects to explain the enhanced sticking. On the other hand, dissociation dynamics at higher incident kinetic energies are strongly dependent on step type. The Pt(553) and Pt(533) surfaces are more reactive than Pt(111), but the (100) step shows higher sticking than the (110) step. We relate this difference to a variation in the effective lowering of the barrier to dissociation from molecularly adsorbed states into atomic states. Our findings are in line with results from experimental desorption studies and theoretical studies of atomic binding energies. We discuss the influence of the different step types on sticking and dissociation dynamics with a one-dimensional potential energy surface.

  11. Dissociative photoionization of β-pinene: an experimental and theoretical study.

    PubMed

    Sheng, Liusi; Cao, Maoqi; Chen, Jun; Fang, Wenzhen; Li, Yuquan; Ge, Shaolin; Shan, Xiaobin; Liu, Fuyi; Zhao, Yujie; Zhenya Wang, Zhenya Wang

    2014-01-01

    We investigated the photoionization and dissociation photoionization of the β-pinene molecular using time-of-flight mass spectrometry with a tunable vacuum ultraviolet source in the region from 8.00eV to 15.50eV. The experimental ionization energy (IE) value is 8.60eV using electron impact as the ionization source which is not in good agreement with theoretical value (8.41 eV) with a G3MP2 method. We obtained the accurate IE of β-pinene (8.45 ± 0.03eV) derived from the efficiency spectrum which is in good agreement with the theoretical value (8.38eV) of the CBS-QB3 method. We elucidated the dissociation pathways of primary fragment ions from the β-pinene cation on the basis of experimental observations in combination with theoretical calculations. Most of the dissociation pathways occur via a rearrangement reaction prior to dissociation. We also determined the structures of the transition states and intermediates for those isomerization processes.

  12. The dissociation of dense liquid nitrogen and shock cooling

    SciTech Connect

    Ross, M.

    1987-07-01

    A theoretical model is used to examine the dissociation of shock-compressed liquid nitrogen. An important feature of the model is the introduction of a binding energy for the atomic state which leads to a volume-dependent dissociation energy. The model correctly predicts the highly unusual feature of shock cooling which is shown to be the consequence of the volume dependent dissociation energy.

  13. Dissociation of ribosomes into large and small subunits.

    PubMed

    Rivera, Maria C; Maguire, Bruce; Lake, James A

    2015-04-01

    Structural and functional studies of ribosomal subunits require the dissociation of intact ribosomes into individual small and large ribosomal subunits. The dissociation of the prokaryotic 70S ribosomes into the 50S and 30S subunits is achieved by dialysis against a buffer containing a lower Mg(2+) concentration. Eukaryotic 80S ribosomes are dissociated into 60S and 40S subunits by incubation in a buffer containing puromycin and higher KCl and Mg(2+) concentrations.

  14. Electron Impact Ionization and Dissociative Ionization of C2H2

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.

    1995-01-01

    By utilizing a crossed electron beam collision geometry, a combination of time-of-flight (TOF) and quadrupole mass spectrometers, and the relative flow technique1 normalized values of cross sections and appearance energies (AP) were obtained for the formation of singly and multiply ionized species resulting from the ionization and dissociation of C2H2. Details ont he apparatus and technique have been published previously.2,3.

  15. Autobiographical memory specificity in dissociative identity disorder.

    PubMed

    Huntjens, Rafaële J C; Wessel, Ineke; Hermans, Dirk; van Minnen, Agnes

    2014-05-01

    A lack of adequate access to autobiographical knowledge has been related to psychopathology. More specifically, patients suffering from depression or a history of trauma have been found to be characterized by overgeneral memory, in other words, they show a relative difficulty in retrieving a specific event from memory located in time and place. Previous studies of overgeneral memory have not included patients with dissociative disorders. These patients are interesting to consider, as they are hypothesized to have the ability to selectively compartmentalize information linked to negative emotions. This study examined avoidance and overgeneral memory in patients with dissociative identity disorder (DID; n = 12). The patients completed the autobiographical memory test (AMT). Their performance was compared with control groups of posttraumatic stress disorder (PTSD) patients (n = 26), healthy controls (n = 29), and DID simulators (n = 26). Specifically, we compared the performance of separate identity states in DID hypothesized to diverge in the use of avoidance as a coping strategy to deal with negative affect. No significant differences in memory specificity were found between the separate identities in DID. Irrespective of identity state, DID patients were characterized by a lack of memory specificity, which was similar to the lack of memory specificity found in PTSD patients. The converging results for DID and PTSD patients add empirical evidence for the role of overgeneral memory involved in the maintenance of posttraumatic psychopathology. PMID:24886016

  16. Autobiographical memory specificity in dissociative identity disorder.

    PubMed

    Huntjens, Rafaële J C; Wessel, Ineke; Hermans, Dirk; van Minnen, Agnes

    2014-05-01

    A lack of adequate access to autobiographical knowledge has been related to psychopathology. More specifically, patients suffering from depression or a history of trauma have been found to be characterized by overgeneral memory, in other words, they show a relative difficulty in retrieving a specific event from memory located in time and place. Previous studies of overgeneral memory have not included patients with dissociative disorders. These patients are interesting to consider, as they are hypothesized to have the ability to selectively compartmentalize information linked to negative emotions. This study examined avoidance and overgeneral memory in patients with dissociative identity disorder (DID; n = 12). The patients completed the autobiographical memory test (AMT). Their performance was compared with control groups of posttraumatic stress disorder (PTSD) patients (n = 26), healthy controls (n = 29), and DID simulators (n = 26). Specifically, we compared the performance of separate identity states in DID hypothesized to diverge in the use of avoidance as a coping strategy to deal with negative affect. No significant differences in memory specificity were found between the separate identities in DID. Irrespective of identity state, DID patients were characterized by a lack of memory specificity, which was similar to the lack of memory specificity found in PTSD patients. The converging results for DID and PTSD patients add empirical evidence for the role of overgeneral memory involved in the maintenance of posttraumatic psychopathology.

  17. Dissociation of methane under high pressure

    NASA Astrophysics Data System (ADS)

    Gao, Guoying; Oganov, Artem R.; Ma, Yanming; Wang, Hui; Li, Peifang; Li, Yinwei; Iitaka, Toshiaki; Zou, Guangtian

    2010-10-01

    Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P212121, Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C2H6) at 95 GPa, butane (C4H10) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune.

  18. Dissociation of methane under high pressure.

    PubMed

    Gao, Guoying; Oganov, Artem R; Ma, Yanming; Wang, Hui; Li, Peifang; Li, Yinwei; Iitaka, Toshiaki; Zou, Guangtian

    2010-10-14

    Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P2(1)2(1)2(1), Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C(2)H(6)) at 95 GPa, butane (C(4)H(10)) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune.

  19. Dissociative phenomena and the question of responsibility.

    PubMed

    Halleck, S L

    1990-10-01

    There are many controversies regarding the prevalence, causation, possible iatrogenicity, and treatment of multiple personality disorder. Those who view the disorder as much more prevalent than has previously been suspected believe it is caused by experiences of severe child abuse and have used rather unorthodox techniques to help the patient relate the experience of abuse to current problems of dissociation. Other clinicians believe the disorder is overdiagnosed and that it may be created or made worse by therapists who unwittingly reinforce symptoms of dissociation. Many of the controversies about these issues can be clarified by considering the manner in which clinicians attribute responsibility for undesirable conduct associated with the disorder. In dealing with multiple personality patients, clinicians regularly must decide whether their therapeutic approach will emphasize the patient's responsibility for undesirable conduct or will minimize it. Practical and theoretical arguments can be made for both approaches. There are important consequences to patients using either approach, and particularly harmful consequences with inconsistent approaches. Clinical experience and wisdom dictate that until we have more objective data about the results of various forms of treatment, the preferred method of treatment of multiple personality patients should continue to focus upon maximizing their responsibility for any type of undesirable conduct.

  20. Vibrational nonequilibrium effects on diatomic dissociation rates

    NASA Technical Reports Server (NTRS)

    Hansen, C. F.

    1993-01-01

    The collision-induced dissociation rate of diatomic molecules from a ladder of rotational and anharmonic vibrational states is developed, and the correction for vibrational nonequilibrium is considered. The result is similar to an analytic correction derived by Hammerling et al. (1959) for harmonic oscillators. An empirical correction algorithm suggested by Park (1987, 1990) gives similar results when vibrational temperature is comparable to kinetic temperature but underestimates the dissociation rate when vibrational temperature is small compared with the kinetic temperature. This algorithm uses an effective temperature in the experimentally determined Arrhenius expression for the rate coefficient, which is a weighted average of the vibrational and kinetic temperature, whereas theory indicates that kinetic temperature should appear only in the exponential term of the Arrhenius expression. Nevertheless, an effective temperature can always be found that will numerically duplicate the proper rate coefficient at any given condition, but a constant weighting factor cannot be expected to provide this. However, the algorithm can he adjusted to give reasonable results over a range of conditions if the geometric weighting factor is taken to be a simple linear function of the ratio of vibrational to kinetic temperature in the gas.

  1. Electron Transfer Dissociation of Milk Oligosaccharides

    NASA Astrophysics Data System (ADS)

    Han, Liang; Costello, Catherine E.

    2011-06-01

    For structural identification of glycans, the classic collision-induced dissociation (CID) spectra are dominated by product ions that derived from glycosidic cleavages, which provide only sequence information. The peaks from cross-ring fragmentation are often absent or have very low abundances in such spectra. Electron transfer dissociation (ETD) is being applied to structural identification of carbohydrates for the first time, and results in some new and detailed information for glycan structural studies. A series of linear milk sugars was analyzed by a variety of fragmentation techniques such as MS/MS by CID and ETD, and MS3 by sequential CID/CID, CID/ETD, and ETD/CID. In CID spectra, the detected peaks were mainly generated via glycosidic cleavages. By comparison, ETD generated various types of abundant cross-ring cleavage ions. These complementary cross-ring cleavages clarified the different linkage types and branching patterns of the representative milk sugar samples. The utilization of different MS3 techniques made it possible to verify initial assignments and to detect the presence of multiple components in isobaric peaks. Fragment ion structures and pathways could be proposed to facilitate the interpretation of carbohydrate ETD spectra, and the main mechanisms were investigated. ETD should contribute substantially to confident structural analysis of a wide variety of oligosaccharides.

  2. Multigenerational Dissociation: A Framework for Building Narrative.

    PubMed

    McCollum, Sally E

    2015-01-01

    This paper presents the concept of Multigenerational Dissociation (MGD), a behavior pattern that occurs in families in which violence and abuse are re-enacted from one generation to the next, accompanied by denial that the trauma occurred, or if it did, that it was destructive. While revictimization, reenactment, and the intergenerational transmission of trauma are discussed extensively in the literature, MGD helps to view them within a broad historical framework. This is useful for conceptualizing cases therapeutically, and it can also contribute to research on dissociation and recovered memories of trauma and abuse by demonstrating the value of narrative clinical data. Case material is used to illustrate how MGD occurs in people's lives and affects their memories, demonstrating how it becomes a frame within which to convey the dynamics of how traumatic experiences are remembered. This also demonstrates that when clinicians contribute their own narrative data to research on traumatic memory, the science is more accurate, relevant, and comprehensible to clinical and nonclinical researchers. PMID:26158318

  3. Dissociable behavioural outcomes of visual statistical learning

    PubMed Central

    Turk-Browne, Nicholas B.; Seitz, Aaron R.

    2016-01-01

    Statistical learning refers to the extraction of probabilistic relationships between stimuli and is increasingly used as a method to understand learning processes. However, numerous cognitive processes are sensitive to the statistical relationships between stimuli and any one measure of learning may conflate these processes; to date little research has focused on differentiating these processes. To understand how multiple processes underlie statistical learning, here we compared, within the same study, operational measures of learning from different tasks that may be differentially sensitive to these processes. In Experiment 1, participants were visually exposed to temporal regularities embedded in a stream of shapes. Their task was to periodically detect whether a shape, whose contrast was staircased to a threshold level, was present or absent. Afterwards, they completed a search task, where statistically predictable shapes were found more quickly. We used the search task to label shape pairs as “learned” or “non-learned”, and then used these labels to analyse the detection task. We found a dissociation between learning on the search task and the detection task where only non-learned pairs showed learning effects in the detection task. This finding was replicated in further experiments with recognition memory (Experiment 2) and associative learning tasks (Experiment 3). Taken together, these findings are consistent with the view that statistical learning may comprise a family of processes that can produce dissociable effects on different aspects of behaviour. PMID:27478399

  4. Dissociative excitation study of iron pentacarbonyl molecule

    NASA Astrophysics Data System (ADS)

    Ribar, Anita; Danko, Marián; Országh, Juraj; Ferreira da Silva, Filipe; Utke, Ivo; Matejčík, Štefan

    2015-04-01

    The processes of dissociative excitation (DE) and dissociative ionisation with excitation (DIE) of iron pentacarbonyl, Fe(CO)5, have been studied using a crossed electron-molecule beam experimental apparatus (Electron Induced Fluorescence Apparatus, EIFA). Using EIFA we were able to record the emission spectrum of the molecule in the UV-VIS range, as well as the photon efficiency curves initiated by electron impact. The emission spectrum of Fe(CO)5 initiated by impact of 50 eV electrons was recorded in the spectral range between 200 nm and 470 nm. It shows a high density of emission lines and bands (mainly iron lines and carbonyl bands). Additionally, we have measured photon efficiency curves (PECs) as a function of the electron impact energy for several lines and bands. On the basis of the PECs we have discussed the reaction mechanism and the energetics of the reactions associated with the DE and DIE processes. Contribution to the Topical Issue "Elementary Processes with Atoms and Molecules in Isolated and Aggregated States", edited by Friedrich Aumayr, Bratislav Marinkovic, Štefan Matejčík, John Tanis and Kurt H. Becker.

  5. Dissociation of methane under high pressure.

    PubMed

    Gao, Guoying; Oganov, Artem R; Ma, Yanming; Wang, Hui; Li, Peifang; Li, Yinwei; Iitaka, Toshiaki; Zou, Guangtian

    2010-10-14

    Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P2(1)2(1)2(1), Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C(2)H(6)) at 95 GPa, butane (C(4)H(10)) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune. PMID:20950018

  6. Dissociative recombination of molecular ions with electrons

    NASA Technical Reports Server (NTRS)

    Johnsen, Rainer

    1990-01-01

    An overview is presented for the present state of the art of laboratory measurements of the dissociative recombination of molecular ions with electrons. Most work has focussed on obtaining rates and their temperature dependence, as these are of primary interest for model calculations of ionospheres. A comparison of data obtained using the microwave afterglow method, the flowing afterglow technique, and the merged beam technique shows that generally the agreement is quite good, but there are some serious discrepancies, especially in the case of H(3+) recombination, that need to be resolved. Results of some earlier experimental work need to be reexamined in the light of more recent developments. Such cases are pointed out and a compilation of rate coefficients that have withstood scrutiny is presented. Recent advances in experimental methods, such as the use of laser-in-duced fluorescence, make it possible to identify some neutral products of dissociative recombination. What has been done so far and what results one might expect from future work are briefly reviewed.

  7. Multigenerational Dissociation: A Framework for Building Narrative.

    PubMed

    McCollum, Sally E

    2015-01-01

    This paper presents the concept of Multigenerational Dissociation (MGD), a behavior pattern that occurs in families in which violence and abuse are re-enacted from one generation to the next, accompanied by denial that the trauma occurred, or if it did, that it was destructive. While revictimization, reenactment, and the intergenerational transmission of trauma are discussed extensively in the literature, MGD helps to view them within a broad historical framework. This is useful for conceptualizing cases therapeutically, and it can also contribute to research on dissociation and recovered memories of trauma and abuse by demonstrating the value of narrative clinical data. Case material is used to illustrate how MGD occurs in people's lives and affects their memories, demonstrating how it becomes a frame within which to convey the dynamics of how traumatic experiences are remembered. This also demonstrates that when clinicians contribute their own narrative data to research on traumatic memory, the science is more accurate, relevant, and comprehensible to clinical and nonclinical researchers.

  8. Effectiveness of treatment for dissociative identity disorder.

    PubMed

    Powell, R A; Howell, A J

    1998-10-01

    In a recent study by Ellason and Ross, patients with Dissociative Identity Disorder reported a decrease in symptoms on the Millon Clinical Multiaxial Inventory-II over a 2-yr. follow-up period. Patients judged to have achieved integration of their personalities rated themselves as more substantially improved on the Millon-II than did patients judged not to have achieved integration. Ellason and Ross suggested that this improvement reflected the influence of treatment; however, for several reasons, their findings are open to alternative interpretations. First, in the absence of proper control conditions, one cannot rule out the contribution of other factors to the over-all improvement of patients such as regression of symptoms toward the mean following the initial assessment. Second, patients self-reported improvement was less substantial when data were reanalyzed using more appropriate statistical criteria. Third, the greater improvement observed among integrated patients relative to nonintegrated patients may reflect influences other than differential responsiveness to treatment, such as less severe pathology prior to treatment. More systematic research is needed to clarify the effect of treatment on Dissociative Identity Disorder.

  9. Dissociative identity disorder and pseudo-hysteria.

    PubMed

    Foote, B

    1999-01-01

    The diagnostic validity of dissociative identity disorder (DID) continues to inspire controversy, with some commentators claiming that DID is a modern variant of "hysteria"; that is, attention-seeking behavior. The author asserts that DID is indeed a valid psychiatric disorder, and believes that this skeptical reaction can largely be attributed to a specific set of transference/countertransference interactions that these patients tend to inspire. The paper delineates several clinical features of DID that can easily be mistaken for hysterical phenomena, and attempts to find the roots of this confusion in the DID patients' experience of interpersonal powerlessness, which leads them to present their symptoms in an unconvincing, "hysterical" manner. Confusion between the vertical split seen in the dissociative disorders and the horizontal split characteristic of the classic hysterical personality is discussed, as is the powerful effect of observer bias in creating hysterical-appearing phenomena. The term "pseudo-hysteria" is used to denote a situation in which a genuine psychiatric disorder, DID, is perceived as an hysterical production.

  10. Frontal and occipital perfusion changes in dissociative identity disorder.

    PubMed

    Sar, Vedat; Unal, Seher N; Ozturk, Erdinc

    2007-12-15

    The aim of the study was to investigate if there were any characteristics of regional cerebral blood flow (rCBF) in dissociative identity disorder. Twenty-one drug-free patients with dissociative identity disorder and nine healthy volunteers participated in the study. In addition to a clinical evaluation, dissociative psychopathology was assessed using the Structured Clinical Interview for DSM-IV Dissociative Disorders, the Dissociative Experiences Scale and the Clinician-Administered Dissociative States Scale. A semi-structured interview for borderline personality disorder, the Hamilton Depression Rating Scale, and the Childhood Trauma Questionnaire were also administered to all patients. Normal controls had to be without a history of childhood trauma and without any depressive or dissociative disorder. Regional cerebral blood flow (rCBF) was studied with single photon emission computed tomography (SPECT) with Tc99m-hexamethylpropylenamine (HMPAO) as a tracer. Compared with findings in the control group, the rCBF ratio was decreased among patients with dissociative identity disorder in the orbitofrontal region bilaterally. It was increased in median and superior frontal regions and occipital regions bilaterally. There was no significant correlation between rCBF ratios of the regions of interest and any of the psychopathology scale scores. An explanation for the neurophysiology of dissociative psychopathology has to invoke a comprehensive model of interaction between anterior and posterior brain regions.

  11. A new view from the acropolis: dissociative identity disorder.

    PubMed

    Brenner, Ira

    2009-01-01

    The author reviews psychoanalytic viewpoints on dissociation and dissociative identity disorder (DID), the controversial condition previously known as multiple personality. He expands his own contributions to the literature over the last fifteen years, incorporating the burgeoning data from research on disturbances of attachment as precursors to dissociation. Utilizing clinical material, he then contrasts DID with trauma and dissociation in adulthood as well as with schizophrenia. He contends that the complexity and myriad manifestations of this condition warrant deeper psychoanalytic exploration to help elucidate not only its true nature, but also to further our understanding of all psychopathology.

  12. The vibrational dynamics of 3D HOCl above dissociation

    SciTech Connect

    Lin, Yi-Der; Reichl, L. E.; Jung, Christof

    2015-03-28

    We explore the classical vibrational dynamics of the HOCl molecule for energies above the dissociation energy of the molecule. Above dissociation, we find that the classical dynamics is dominated by an invariant manifold which appears to stabilize two periodic orbits at energies significantly above the dissociation energy. These stable periodic orbits can hold a large number of quantum states and likely can support a significant quasibound state of the molecule, well above the dissociation energy. The classical dynamics and the lifetime of quantum states on the invariant manifold are determined.

  13. Dissociation curves of diatomic molecules: A DC-DFT study

    SciTech Connect

    Sim, Eunji; Kim, Min-Cheol; Burke, Kieron

    2015-12-31

    We investigate dissociation of diatomic molecules using standard density functional theory (DFT) and density-corrected density functional theory (DC-DFT) compared with CCSD(T) results as reference. The results show the difference between the HOMO values of dissociated atomic species often can be used as an indicator whether DFT would predict the correct dissociation limit. DFT predicts incorrect dissociation limits and charge distribution in molecules or molecular ions when the fragments have large HOMO differences, while DC-DFT and CCSD(T) do not. The criteria for large HOMO difference is about 2 ∼ 4 eV.

  14. Dissociative disorders in Turkish inpatients with conversion disorder.

    PubMed

    Tezcan, Ertan; Atmaca, Murad; Kuloglu, Murat; Gecici, Omer; Buyukbayram, Ayten; Tutkun, Hamdi

    2003-01-01

    The aim of our study was to determine the frequency of dissociative disorders (DDs) among inpatients with conversion disorder (CD) in a university clinic settled in Eastern Turkey. During a period of 24 months, 59 consecutively admitted adult CD patients were screened with the Dissociative Experience Scale (DES). Patients who scored above 30 (DDs group) did not differ by age or gender from a group of inpatients who scored below 10 on the scale (comparison group). All patients in the two groups were then interviewed in a blind manner using the Dissociative Disorders Interview Schedule (DDIS) and Structured Interview for DSM-IV Dissociative Disorders (SCID-D). According to the SCID-D, 18 of 59 patients (30.5%) received a diagnosis of dissociative disorder; nine of these 18 patients (50%) were diagnosed as having dissociative identity disorder, eight (44.4%) were diagnosed as having dissociative disorder not otherwise specified (NOS), and one (5.6%) was diagnosed as having dissociative amnesia. Accordingly to the DDIS, borderline personality disorder was frequent in the DDs group, and all of the patients in the DDs group reported sexual abuse and neglect during childhood, latency, or adolescence. A high proportion of CD patients have significant dissociative pathology. The proper diagnosis of these patients has important implications for their clinical course.

  15. Dissociability of free and peptidyl-tRNA bound ribosomes.

    PubMed

    Surguchov, A P; Fominykch, E S; Lyzlova, L V

    1978-06-16

    The influence of peptidyl-tRNA on the dissociation of yeast 80 S ribosomes into subunits was studied. For this purpose temperature-sensitive (ts) suppressor strain of yeast Saccharomyces cervisiae carrying a defect in peptide chain termination was used. It was found that peptidyl-tRNA did not influence the dissociation of ribosomes either at high salt concentration or in the presence of dissociation factor (DF) from yeast. After dissociation of yeast ribosomes in 0.5 M KCl, peptidyl-tRNA remains bound to the 60 S subunit. Some characteristics of the termination process and release of nascent polypeptides from yeast ribosomes are discussed. PMID:355860

  16. Examination of the pathological dissociation taxon in depersonalization disorder.

    PubMed

    Simeon, Daphne; Knutelska, Margaret; Nelson, Dorothy; Guralnik, Orna; Schmeidler, James

    2003-11-01

    In recent years, the pathologic dissociation taxon developed by Waller, Putnam, and Carlson (Psychological Methods 1:300-321, 1996) from a Dissociative Identity Disorder (DID) sample has been increasingly used in studies of dissociation in general. However, the taxon's convergence with dissociative diagnoses other than DID, as well as the taxon's central premise that pathologic dissociation is a categorical rather than a dimensional construct, remain areas of exploration. This report examines the applicability of the pathologic dissociation taxon to Depersonalization Disorder (DPD). The Dissociative Experiences Scale was administered to 100 consecutively recruited DPD subjects diagnosed by semistructured clinical interview and by the SCID-D. Taxon membership probability was calculated using the recommended SAS scoring program. Approximately 2/3 of subjects (N = 64) had a very high probability (>.80) of belonging to the taxon, while 1/3 of subjects had a very low probability (<.10) of belonging to the taxon. A taxon cutoff score of 13 yielded an 81% sensitivity in detecting the presence of DPD. The modest convergence between taxonic membership and clinical dissociative disorder diagnosis suggests that the taxon may have important limitations in its use, at least when applied to DPD in its current form. As previously, we continue to recommend a low taxon cutoff score (13) for the sensitive detection of depersonalization disorder. The inference that pathologic dissociation is a unitary and categorical entity is also discussed.

  17. Psychometric validation of the State Scale of Dissociation (SSD).

    PubMed

    Krüger, Christa; Mace, Chris J

    2002-03-01

    Although dissociative phenomena are often transient features of mental states, existing measures of dissociation are designed to measure enduring traits. A new present-state self-report measure, sensitive to changes in dissociative states, was therefore developed and psychometrically validated. Fifty-six items were formulated to measure state features, and sorted according to seven subscales: derealization, depersonalization, identity confusion, identity alteration, conversion, amnesia and hypermnesia. The State Scale of Dissociation (SSD) was administered with other psychiatric scales (DES, BDI, BAI, SCI-PANSS) to 130 participants with DSM-IV major depressive disorder schizophrenia, alcohol withdrawal, dissociative disorders and controls. In these sample populations, the SSD was demonstrated as a valid and reliable measure of changes in and the severity of dissociative states. Discriminant validity, content, concurrent, predictive, internal criterion-related, internal construct and convergent validities, and internal consistency and split-half reliability were confirmed statistically. Clinical observations of dissociative states, and their comorbidity with symptoms of depression and psychotic illness, were confirmed empirically. The SSD, an acceptable, valid and reliable scale measuring state features of dissociation at the time of completion, was obtained. This is a prerequisite for further investigation of correlations between changes in dissociative states and concurrent physiological parameters.

  18. Dissociation energy and dynamics of water clusters

    NASA Astrophysics Data System (ADS)

    Ch'ng, Lee Chiat

    The state-to-state vibrational predissociation (VP) dynamics of water clusters were studied following excitation of a vibrational mode of each cluster. Velocity-map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated center-of-mass translational energy distributions. Product energy distributions and dissociation energies were determined. Following vibrational excitation of the HCl stretch fundamental of the HCl-H2O dimer, HCl fragments were detected by 2 + 1 REMPI via the f 3□2(nu' = 0) ← X 1Sigma+(nu'' = 0) and V1Sigma + (nu' = 11 and 12) ← X1Sigma+ (nu'' = 0) transitions. REMPI spectra clearly show HCl from dissociation produced in the ground vibrational state with J'' up to 11. The fragments' center-of-mass translational energy distributions were determined from images of selected rotational states of HCl and were converted to rotational state distributions of the water cofragment. All the distributions could be fit well when using a dimer dissociation energy of bond dissociation energy D0 = 1334 +/- 10 cm--1. The rotational distributions in the water cofragment pair-correlated with specific rotational states of HCl appear nonstatistical when compared to predictions of the statistical phase space theory. A detailed analysis of pair-correlated state distributions was complicated by the large number of water rotational states available, but the data show that the water rotational populations increase with decreasing translational energy. H2O fragments of this dimer were detected by 2 + 1 REMPI via the C˜1B1(000) ← X˜1A1(000) transition. REMPI clearly shows that H2O from dissociation is produced in the ground vibrational state. The fragment's center-of-mass translational energy distributions were determined from images of selected rotational states of H2O and were converted to rotational state distributions of the HCl cofragment. The distributions gave D0 = 1334 +/- 10 cm --1 and show a clear

  19. Products of Dissociative Recombination in the Ionosphere

    NASA Technical Reports Server (NTRS)

    Cosby, Philip

    1996-01-01

    SRI International undertook a novel experimental measurement of the product states formed by dissociative recombination (DR) of O2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and rovibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates. For a molecular ion such as O2(+), the dissociation recombination reaction is (1) O2(+) + e yields O + O + W. The atomic products of this reaction, in this case two oxygen atoms, can be produced in a variety of excited states and with a variety of kinetic energies, as represented by W in Eq. (1). These atoms are not only active in the neutral chemistry of the ionosphere, but are also especially important because their optical emissions are often used to infer in situ concentrations of the parent molecular ion and ambient electron densities. Many laboratory measurements have been made of DR reaction rates under a wide range of electron temperatures, but very little is known about the actual distributions among the final states of the atomic products. This lack of knowledge seriously limits the validity and effectiveness of efforts to model both natural and man-made ionospheric disturbances. Bates recently identified major deficiencies in the currently accepted branching ratios for O2(+) as they relate to blue and green line emission measurements in the nocturnal F-region. During our two-year effort, we partially satisfied our ambitious goals. We constructed and operated a variable pressure, electron-impact ion source and a high pressure, hollow-cathode discharge ion

  20. Controls on Gas Hydrate Formation and Dissociation

    SciTech Connect

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  1. Development of the Hebrew-Multidimensional Inventory of Dissociation (H-MID): a valid and reliable measure of pathological dissociation.

    PubMed

    Somer, Eli; Dell, Paul F

    2005-01-01

    The Multidimensional Inventory of Dissociation (MID; Dell, 2004b) has 168 dissociation items and 50 validity items. The MID assesses 14 major facets of dissociation, 23 symptoms of dissociation, and has 5 validity scales. The MID operationalizes (a) the subjective/ phenomenological domain of dissociation, and (b) 23 hypothesized symptoms of dissociative identity disorder (DID). This article describes the development of a Hebrew version of the MID (H-MID). In a sample of clinical and nonclinical research participants, the H-MID had strong internal consistency, temporal stability, and strong structural, convergent, discriminant, and construct validity. In addition, mean H-MID scores demonstrated incremental validity over the Hebrew Dissociative Experiences Scale (H-DES) by predicting an additional 17% of the variance in weighted trauma scores on the Traumatic Experiences Questionnaire (TEQ). Factor analysis of the H-MID extracted a single factor: dissociation. Both the MID and the subjective/phenomenological concept of pathological dissociation appear to have applicability not only in North America, but also in a heterogeneous Middle Eastern culture.

  2. Interidentity memory transfer in dissociative identity disorder.

    PubMed

    Kong, Lauren L; Allen, John J B; Glisky, Elizabeth L

    2008-08-01

    Controversy surrounding dissociative identity disorder (DID) has focused on conflicting findings regarding the validity and nature of interidentity amnesia, illustrating the need for objective methods of examining amnesia that can discriminate between explicit and implicit memory transfer. In the present study, the authors used a cross-modal manipulation designed to mitigate implicit memory effects. Explicit memory transfer between identities was examined in 7 DID participants and 34 matched control participants. After words were presented to one identity auditorily, the authors tested another identity for memory of those words in the visual modality using an exclusion paradigm. Despite self-reported interidentity amnesia, memory for experimental stimuli transferred between identities. DID patients showed no superior ability to compartmentalize information, as would be expected with interidentity amnesia. The cross-modal nature of the test makes it unlikely that memory transfer was implicit. These findings demonstrate that subjective reports of interidentity amnesia are not necessarily corroborated by objective tests of explicit memory transfer.

  3. Dissociative electron attachment studies on acetone

    SciTech Connect

    Prabhudesai, Vaibhav S. Tadsare, Vishvesh; Ghosh, Sanat; Gope, Krishnendu; Davis, Daly; Krishnakumar, E.

    2014-10-28

    Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels in the electron energy range of 0–20 eV. H{sup −} is found to be the most dominant fragment followed by O{sup −} and OH{sup −} with only one resonance peak between 8 and 9 eV. The DEA dynamics is studied by measuring the angular distribution and kinetic energy distribution of fragment anions using Velocity Slice Imaging technique. The kinetic energy and angular distribution of H{sup −} and O{sup −} fragments suggest a many body break-up for the lone resonance observed. The ab initio calculations show that electron is captured in the multi-centered anti-bonding molecular orbital which would lead to a many body break-up of the resonance.

  4. Copper dissociation from estuarine humic materials

    NASA Astrophysics Data System (ADS)

    Olson, Dean L.; Shuman, Mark S.

    1985-06-01

    Dissolved humic material from three locations on the Ogeechee River Estuary near Savannah, GA, was ultrafiltered into three size fractions and used for kinetic experiments with Cu(II). A Cu(II)-humic mixture was reacted with a colorimetric reagent for Cu(II) and absorbance observed from 50 msec to at least 1835 sec corresponding to rate constants from 0.001-40 sec -1. The apparent dissociation rate constants were distributed over a wide range, with most bound Cu(II) having k > 1 sec-1 ( t 1/2 < 0.7 sec ). Nearly all the variation seen in the kinetic distribution was among size fractions; as size fraction decreased, the distribution of bound Cu(II) shifted to larger rate constants. Location of sampling stations on the estuary had little effect on results.

  5. Exciton transport and dissociation at organic interfaces

    NASA Astrophysics Data System (ADS)

    Beljonne, David

    2011-03-01

    This paper focuses on modeling studies of exciton transport and dissociation at organic interfaces and includes three parts: 1) Experiments have shown that the values of exciton diffusion length LD in conjugated polymers (CPs) are rather low, in the range of 5-10 nm, apparently regardless of their chemical structure and solid-state packing. In contrast, larger LD values have been reported in molecular materials that are chemically more well-defined than CPs. Here we demonstrate that energetic disorder alone reduces the exciton diffusion length more than one order of magnitude, from values typically encountered in molecules (> 50nm) to values actually measured in CPs (<10nm). 2) A number of organic crystals show anisotropic excitonic couplings, with weak interlayer interactions between molecules that are more strongly coupled within the layers. The resulting energy carriers are intra-layer 2D excitons that diffuse along the interlayer direction. We model this analytically for infinite layers and using quantum-chemical calculations of the electronic couplings for anthracene clusters. We show that the exciton hopping rates and diffusion lengths depend in a subtle manner on the size and shape of the interacting aggregates, temperature and the presence of energetic disorder. 3) The electronic structure at organic/organic interfaces plays a key role, among others, in defining the quantum efficiency of organic-based photovoltaic cells. Here, we perform quantum-chemical and microelectrostatic calculations on molecular aggregates of various sizes and shapes to characterize the interfacial dipole moment at pentacene/C60 heterojunctions. The results show that the interfacial dipole mostly originates in polarization effects due to the asymmetry in the multipolar expansion of the electronic density distribution between the interacting molecules. We will discuss how the quadrupoles on the pentacene molecules produce direct electrostatic interactions with charge carriers and how

  6. The rise and fall of dissociative identity disorder.

    PubMed

    Paris, Joel

    2012-12-01

    Dissociative identity disorder (DID), once considered rare, was frequently diagnosed during the 1980s and 1990s, after which interest declined. This is the trajectory of a medical fad. DID was based on poorly conceived theories and used potentially damaging treatment methods. The problem continues, given that the DSM-5 includes DID and accords dissociative disorders a separate chapter in its manual. PMID:23197123

  7. 21 CFR 886.1910 - Spectacle dissociation test system.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Spectacle dissociation test system. 886.1910 Section 886.1910 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1910 Spectacle dissociation test system. (a) Identification. A...

  8. Effect of dissociation on thermodynamic properties of pure diatomic gases

    NASA Technical Reports Server (NTRS)

    Woolley, Harold W

    1955-01-01

    A graphical method is described by which the enthalpy, entropy, and compressibility factor for the equilibrium mixture of atoms and diatomic molecules for pure gaseous elements may be obtained and shown for any dissociating element for which the necessary data exist. Results are given for hydrogen, oxygen, and nitrogen. The effect of dissociation on the heat capacity is discussed briefly.

  9. The rise and fall of dissociative identity disorder.

    PubMed

    Paris, Joel

    2012-12-01

    Dissociative identity disorder (DID), once considered rare, was frequently diagnosed during the 1980s and 1990s, after which interest declined. This is the trajectory of a medical fad. DID was based on poorly conceived theories and used potentially damaging treatment methods. The problem continues, given that the DSM-5 includes DID and accords dissociative disorders a separate chapter in its manual.

  10. Errors of Logic and Scholarship Concerning Dissociative Identity Disorder

    ERIC Educational Resources Information Center

    Ross, Colin A.

    2009-01-01

    The author reviewed a two-part critique of dissociative identity disorder published in the "Canadian Journal of Psychiatry". The two papers contain errors of logic and scholarship. Contrary to the conclusions in the critique, dissociative identity disorder has established diagnostic reliability and concurrent validity, the trauma histories of…

  11. Memory Abilities in Williams Syndrome: Dissociation or Developmental Delay Hypothesis?

    ERIC Educational Resources Information Center

    Sampaio, Adriana; Sousa, Nuno; Fernandez, Montse; Henriques, Margarida; Goncalves, Oscar F.

    2008-01-01

    Williams syndrome (WS) is a neurodevelopmental genetic disorder often described as being characterized by a dissociative cognitive architecture, in which profound impairments of visuo-spatial cognition contrast with relative preservation of linguistic, face recognition and auditory short-memory abilities. This asymmetric and dissociative cognition…

  12. Switch Function and Pathological Dissociation in Acute Psychiatric Inpatients

    PubMed Central

    Chiu, Chui-De; Tseng, Mei-Chih Meg; Chien, Yi-Ling; Liao, Shih-Cheng; Liu, Chih-Min; Yeh, Yei-Yu; Hwu, Hai-Gwo

    2016-01-01

    Swift switching, along with atypical ability on updating and inhibition, has been found in non-clinical dissociators. However, whether swift switching is a cognitive endophenotype that intertwines with traumatisation and pathological dissociation remains unknown. Unspecified acute psychiatric patients were recruited to verify a hypothesis that pathological dissociation is associated with swift switching and traumatisation may explain this relationship. Behavioural measures of intellectual function and three executive functions including updating, switching and inhibition were administered, together with standardised scales to evaluate pathological dissociation and traumatisation. Our results showed superior control ability on switching and updating in inpatients who displayed more symptoms of pathological dissociation. When all three executive functions were entered as predictors, in addition to intellectual quotient and demographic variables to regress upon pathological dissociation, switching rather than updating remained the significant predictor. Importantly, the relationship between pathological dissociation and switching became non-significant when the effect of childhood trauma were controlled. The results support a trauma-related switching hypothesis which postulates swift switching as a cognitive endophenotype of pathological dissociation; traumatisation in childhood may explain the importance of swift switching. PMID:27123578

  13. Dissociative Disorders in Children: Behavioral Profiles and Problems.

    ERIC Educational Resources Information Center

    Putnam, Frank W.

    1993-01-01

    Clinical research has established a connection between childhood trauma and the development of dissociative disorders in adults. Pathological dissociation produces a range of symptoms and behaviors such as amnesias, rapid shifts in mood and behavior, and auditory and visual hallucinations. Many of these symptoms are misdiagnosed as attention,…

  14. Self-Destructive Behavior in People with Dissociative Disorders.

    ERIC Educational Resources Information Center

    Saxe, Glenn N.; Chawla, Neharika; Van der Kolk, Bessel

    2002-01-01

    Study assesses self-destructive behavior in a group of inpatients who have dissociative disorders compared to those who report few dissociative symptoms. Results reveal that these patients more frequently engage in self-destructive behaviors, use more methods of self-injury, and begin to injure themselves at an earlier age then patients who do not…

  15. RAIRS observation of photoinduced dissociation of NO on Ni(111)

    NASA Astrophysics Data System (ADS)

    Magkoev, Tamerlan T.; Song, Moon-Bong; Fukutani, Katsuyuki; Murata, Yoshitada

    1995-06-01

    The properties of the {NO}/{Ni(111) } system under nanosecond ultraviolet laser light irradiation are studied by reflection absorption infrared spectroscopy. It is found that adsorbed NO molecules are dissociated by laser light. Dissociation proceeds effectively in a dilute NO layer, whereas it is suppressed in a saturated overlayer.

  16. Dissociative Spectrum Disorders in the Primary Care Setting.

    PubMed

    Elmore, James L.

    2000-04-01

    Dissociative disorders have a lifetime prevalence of about 10%. Dissociative symptoms may occur in acute stress disorder, posttraumatic stress disorder, somatization disorder, substance abuse, trance and possession trance, Ganser's syndrome, and dissociative identity disorder, as well as in mood disorders, psychoses, and personality disorders. Dissociative symptoms and disorders are observed frequently among patients attending our rural South Carolina community mental health center. Given the prevalence of mental illness in primary care settings and the diagnostic difficulties encountered with dissociative disorders, such illness may be undiagnosed or misdiagnosed in primary care settings. We developed an intervention model that may be applicable to primary care settings or helpful to primary care physicians. Key points of the intervention are identification of dissociative symptoms, patient and family education, review of the origin of the symptoms as a method of coping with trauma, and supportive reinforcement of cognitive and relaxation skills during follow-up visits. Symptom recognition, Education of the family, Learning new skills, and Follow-up may be remembered by the mnemonic device SELF. We present several cases to illustrate dissociative symptoms and our intervention. Physicians and other professionals using the 4 steps and behavioral approaches will be able to better recognize and triage patients with dissociative symptoms. Behaviors previously thought to be secondary to psychosis or personality disorders may be seen in a new frame of reference, strengthening the therapeutic alliance while reducing distress and acting-out behaviors.

  17. Dissociative Symptoms and Mother's Marital Status in Young Adult Population

    PubMed Central

    Bob, Petr; Selesova, Petra; Raboch, Jiri; Kukla, Lubomir

    2015-01-01

    Abstract Current findings suggest that mother's marital status indicating father's absence or conflicting relationship to father may be specifically related to dissociation and other stress-related symptoms. We have assessed relationships of mother's marital status, dissociative symptoms, and other psychopathological manifestations in a sample of 19 years’ old young adults (N = 364) participating in European longitudinal study (European Longitudinal Study of Parenthood and Childhood). The results show clinically significant manifestations of dissociative symptoms in young adult men whose mothers were fatherless and in women whose mothers were re-married. Other psychopathological symptoms did not reach clinically significant manifestations. The results suggest that significant factor related to high level of dissociative symptoms in men growing in fatherless families might be linked with disturbed and conflicting attachment to a father's figure and pathological dependent attachment to mother. In women dissociative symptoms likely are linked to conflicting relationship between mother and daughter associated with stepfather’ presence in the family. PMID:25590849

  18. Unresolved mourning, supernatural beliefs and dissociation: a mediation analysis.

    PubMed

    Thomson, Paula; Jaque, S Victoria

    2014-01-01

    Unresolved mourning is marked by disorganized behavior and states of mind. In this study, we speculated that pathological dissociation would mediate the effects of unresolved mourning on supernatural beliefs. This hypothesis was determined based on findings that indicate an association between higher levels of dissociation, stronger beliefs in the supernatural and unresolved mourning. We examined two groups of participants, one classified as non-unresolved (non-U) (n = 56) and the other as unresolved (n = 26) (U) with respect to past loss/trauma as measured by the Adult Attachment Interview (AAI). Two self-report instruments were administered to measure supernatural beliefs and dissociation. As hypothesized, the multivariate analysis of variance indicated mean differences between the two groups. The unresolved group had greater belief in the supernatural and more pathological dissociative processes. The mediation analysis demonstrated that pathological dissociation fully mediated the effects of unresolved mourning on supernatural beliefs. PMID:24913392

  19. The dissociative character: a reconsideration of "multiple personality".

    PubMed

    Brenner, I

    1994-01-01

    The author has interviewed and reviewed the cases of over 100 patients with a suspected diagnosis of multiple personality disorder (MPD). He finds it clinically useful to think of a continuum of character pathology in which dissociative and defensive altered states predominate. At one end of this continuum is MPD, which he considers a lower-level dissociative character. He redefines dissociation as a defensive altered state, due to autohypnosis, which augments repression or splitting. Depending on the degree of integration of the ego, it may result in a broad range of disturbances of alertness, awareness, memory, and identity. Four vignettes are presented which illustrate a transient hypnoid state, "characterological" dissociation in an upper-level dissociative character, and two cases of MPD, including one emerging in analysis.

  20. Trauma-related dissociative (conversion) disorders in children and adolescents--an overview of assessment tools and treatment principles.

    PubMed

    Diseth, Trond H; Christie, Helen J

    2005-01-01

    A high proportion of patients in child and adolescent psychiatry with significant dissociative symptomatology after early childhood traumatization may go undiagnosed, be wrongly diagnosed and/or inappropriately treated. The diagnostics and treatment of dissociative disorders have been limited by lack of comprehensive, reliable and valid instruments and the ongoing polarization and fierce controversy regarding treatment. However, recent neurobiological findings of neurochemical, functional and structural cerebral consequences of early stressful childhood experiences point out a need for active, early and effective identification and treatment interventions. We present an update on assessment tools available in the Nordic countries, and an overview of different appropriate therapeutic intervention models for children and adolescents. A systematic overview of studies of dissociation in children and adolescent published over the last decade disclosed a total of 1019 references. The 465 papers describing aspects of assessment tools and/or treatment were studied in detail. Reliable and valid screening questionnaires and diagnostic interviews for children and adolescents now allow for effective early identification of dissociative disorders. A combination of individual psychotherapy, pharmacotherapy and family therapy are often required to handle dissociative disorders in children and adolescents. Cognitive-behavioural therapy, hypnotherapy, Eye-Movement Desensitization-Reprocessing (EMDR), psychodynamic therapy and an integrated approach are the main described psychotherapeutic approaches, but treatment of dissociation in children and adolescent does not require allegiance to any one particular treatment model. However, achievement of physical safety by providing a safe environment is a primary goal that supersedes any other therapeutic work. Assessments tools are now available, and appropriate therapeutic intervention models may hopefully contribute to reduce the risk

  1. A structural view of the dissociation of Escherichia coli tryptophanase.

    PubMed

    Green, Keren; Qasim, Nasrin; Gdaelvsky, Garik; Kogan, Anna; Goldgur, Yehuda; Parola, Abraham H; Lotan, Ofra; Almog, Orna

    2015-12-01

    Tryptophanase (Trpase) is a pyridoxal 5'-phosphate (PLP)-dependent homotetrameric enzyme which catalyzes the degradation of L-tryptophan. Trpase is also known for its cold lability, which is a reversible loss of activity at low temperature (2°C) that is associated with the dissociation of the tetramer. Escherichia coli Trpase dissociates into dimers, while Proteus vulgaris Trpase dissociates into monomers. As such, this enzyme is an appropriate model to study the protein-protein interactions and quaternary structure of proteins. The aim of the present study was to understand the differences in the mode of dissociation between the E. coli and P. vulgaris Trpases. In particular, the effect of mutations along the molecular axes of homotetrameric Trpase on its dissociation was studied. To answer this question, two groups of mutants of the E. coli enzyme were created to resemble the amino-acid sequence of P. vulgaris Trpase. In one group, residues 15 and 59 that are located along the molecular axis R (also termed the noncatalytic axis) were mutated. The second group included a mutation at position 298, located along the molecular axis Q (also termed the catalytic axis). Replacing amino-acid residues along the R axis resulted in dissociation of the tetramers into monomers, similar to the P. vulgaris Trpase, while replacing amino-acid residues along the Q axis resulted in dissociation into dimers only. The crystal structure of the V59M mutant of E. coli Trpase was also determined in its apo form and was found to be similar to that of the wild type. This study suggests that in E. coli Trpase hydrophobic interactions along the R axis hold the two monomers together more strongly, preventing the dissociation of the dimers into monomers. Mutation of position 298 along the Q axis to a charged residue resulted in tetramers that are less susceptible to dissociation. Thus, the results indicate that dissociation of E. coli Trpase into dimers occurs along the molecular Q axis.

  2. Gas-Phase Dissociation Pathways of Multiply Charged Peptide Clusters

    PubMed Central

    Jurchen, John C.; Garcia, David E.; Williams, Evan R.

    2005-01-01

    Numerous studies of cluster formation and dissociation have been conducted to determine properties of matter in the transition from the condensed phase to the gas phase using materials as diverse as atomic nuclei, noble gasses, metal clusters, and amino acids. Here, electrospray ionization is used to extend the study of cluster dissociation to peptides including leucine enkephalin with 7–19 monomer units and 2–5 protons, and somatostatin with 5 monomer units and 4 protons under conditions where its intramolecular disulfide bond is either oxidized or reduced. Evaporation of neutral monomers and charge separation by cluster fission are the competing dissociation pathways of both peptides. The dominant fission product for all leucine enkephalin clusters studied is a proton-bound dimer, presumably due to the high gas-phase stability of this species. The branching ratio of the fission and evaporation processes for leucine enkephalin clusters appears to be determined by the value of z2/n for the cluster where z is the charge and n the number of monomer units in the cluster. Clusters with low and high values of z2/n dissociate primarily by evaporation and cluster fission respectively, with a sharp transition between dissociation primarily by evaporation and primarily by fission measured at a z2/n value of ~0.5. The dependence of the dissociation pathway of a cluster on z2/n is similar to the dissociation of atomic nuclei and multiply charged metal clusters indicating that leucine enkephalin peptide clusters exist in a state that is more disordered, and possibly fluid, rather than highly structured in the dissociative transition state. The branching ratio, but not the dissociation pathway of [somatostatin5 + 4H]4+ is altered by the reduction of its internal disulfide bond indicating that monomer conformational flexibility plays a role in peptide cluster dissociation. PMID:14652186

  3. Dissociative, depressive, and PTSD symptom severity as correlates of nonsuicidal self-injury and suicidality in dissociative disorder patients.

    PubMed

    Webermann, Aliya R; Myrick, Amie C; Taylor, Christina L; Chasson, Gregory S; Brand, Bethany L

    2016-01-01

    The present study investigates whether symptom severity can distinguish patients diagnosed with dissociative identity disorder and dissociative disorder not otherwise specified with a recent history of nonsuicidal self-injury (NSSI) and suicide attempts from those patients without recent self-harm. A total of 241 clinicians reported on recent history of patient NSSI and suicide attempts. Of these clinicians' patients, 221 completed dissociative, depressive, and posttraumatic stress disorder symptomatology measures. Baseline cross-sectional data from a naturalistic and prospective study of dissociative disorder patients receiving community treatment were utilized. Analyses evaluated dissociative, depressive, and posttraumatic stress disorder symptom severity as methods of classifying patients into NSSI and suicide attempt groupings. Results indicated that dissociation severity accurately classified patients into NSSI and suicidality groups, whereas depression severity accurately classified patients into NSSI groups. These findings point to dissociation and depression severity as important correlates of NSSI and suicidality in patients with dissociative disorders and have implications for self-harm prevention and treatment. PMID:26211678

  4. Testing the diagnosis of dissociative identity disorder through measures of dissociation, absorption, hypnotizability and PTSD: a Norwegian pilot study.

    PubMed

    Dale, Karl Yngvar; Berg, Renate; Elden, Ake; Ødegård, Atle; Holte, Arne

    2009-01-01

    A total of 14 women meeting criteria for dissociative identity disorder (DID) based on the Diagnostic and Statistical Manual of Mental Disorders (4th ed. [DSM-IV]) were compared to a group of women (n = 10) with other dissociative diagnoses and a group of normal controls (n = 14) with regard to dissociativity, absorption, trauma related symptoms and hypnotizability. Both of the clinical groups reported histories of childhood trauma and attained high PTSD scores. The DID group differed significantly from the group with other dissociative diagnoses and the non-diagnosed comparison group with regard to hypnotizability, the variety of dissociative symptomatology, and the magnitude of dissociative symptomatology. However, no significant differences between the two clinical groups were detected with regard to absorption, general dissociative level, or symptoms related to traumatic stress. Results support the notion that DID can be regarded as a clinical entity which is separable from other dissociative disorders. Results also indicated that hypnotizability is the most important clinical feature of DID.

  5. Dissociative, depressive, and PTSD symptom severity as correlates of nonsuicidal self-injury and suicidality in dissociative disorder patients.

    PubMed

    Webermann, Aliya R; Myrick, Amie C; Taylor, Christina L; Chasson, Gregory S; Brand, Bethany L

    2016-01-01

    The present study investigates whether symptom severity can distinguish patients diagnosed with dissociative identity disorder and dissociative disorder not otherwise specified with a recent history of nonsuicidal self-injury (NSSI) and suicide attempts from those patients without recent self-harm. A total of 241 clinicians reported on recent history of patient NSSI and suicide attempts. Of these clinicians' patients, 221 completed dissociative, depressive, and posttraumatic stress disorder symptomatology measures. Baseline cross-sectional data from a naturalistic and prospective study of dissociative disorder patients receiving community treatment were utilized. Analyses evaluated dissociative, depressive, and posttraumatic stress disorder symptom severity as methods of classifying patients into NSSI and suicide attempt groupings. Results indicated that dissociation severity accurately classified patients into NSSI and suicidality groups, whereas depression severity accurately classified patients into NSSI groups. These findings point to dissociation and depression severity as important correlates of NSSI and suicidality in patients with dissociative disorders and have implications for self-harm prevention and treatment.

  6. Observation of the dynamics leading to a conical intersection in dissociative electron attachment to water

    SciTech Connect

    Haxton, Dan; Adaniya, Hidihito; Slaughter, Dan; Rudek, B.; Osipov, Timur; Weber, Thorsten; Rescigno, Tom; McCurdy, Bill; Belkacem, Ali

    2011-06-08

    Following prior work on the lower-energy resonances, we apply techniques of momentum imaging and ab initio scattering calculations to the process of dissociative electron attachment to water via the highest-energy {sup 2}B{sub 2} resonance. We focus on the H{sup -} anion fragment, which is produced via dynamics passing through and avoiding the conical intersection with the lower A{sub 1} state, leading to OH ((sup 2}{Pi} ) and OH ({sup 2}{Sigma} ), respectively. The momentum imaging technique, when combined with theoretical calculations on the attachment amplitude and dissociation dynamics, demonstrates that the angular distributions provide a signature of the location of the conical intersection in the space of nuclear con gurations.

  7. Chiral Differentiation of Amino Acids by In-Source Collision-Induced Dissociation Mass Spectrometry.

    PubMed

    Kong, Xianglei; Huo, Zhaiyi; Zhai, Wei

    2014-01-01

    Chiral recognition of d- and l-amino acids is achieved by a method combining electrospray ionization (ESI) and in-source collision-induced dissociation (CID) mass spectrometry (MS). Trimeric cluster ions [Cu(II)(A)(ref)2-H](+) are formed by ESI of mixtures of d- or l-analyte amino acid (A), chiral reference (ref) and CuSO4. By increasing the applied voltage in the ESI source region, the trimeric ions become unstable and dissociate progressively. Thus chiral differentiation of the analyte can be achieved by comparing the dependence of their relative intensities to a reference ion on applied voltages. The method does not need MS/MS technique, thus can be readily performed on single-stage MS instruments by turning the voltage of sampling cone.

  8. Transfer of newly acquired stimulus valence between identities in dissociative identity disorder (DID).

    PubMed

    Huntjens, Rafaële J C; Peters, Madelon L; Postma, Albert; Woertman, Liesbeth; Effting, Marieke; van der Hart, Onno

    2005-02-01

    Patients with Dissociative Identity Disorder (DID) frequently report episodes of interidentity amnesia, that is amnesia for events experienced by other identities. The goal of the present experiment was to test the implicit transfer of trauma-related information between identities in DID. We hypothesized that whereas declarative information may transfer from one identity to another, the emotional connotation of the memory may be dissociated, especially in the case of negative, trauma-related emotional valence. An evaluative conditioning procedure was combined with an affective priming procedure, both performed by different identities. In the evaluative conditioning procedure, previously neutral stimuli come to refer to a negative or positive connotation. The affective priming procedure was used to test the transfer of this acquired valence to an identity reporting interidentity amnesia. Results indicated activation of stimulus valence in the affective priming task, that is transfer of emotional material between identities.

  9. Observation of the dynamics leading to a conical intersection in dissociative electron attachment to water

    SciTech Connect

    Haxton, D.; Adaniya, H.; Slaughter, D. S.; Rudek, B.; Osipov, T.; Weber, T.; Rescigno, T. N.; McCurdy, C. W.; Belkacem, A.

    2011-08-11

    Following prior work on the lower-energy resonances, we apply techniques of momentum imaging and ab initio scattering calculations to the process of dissociative electron attachment to water via the highest-energy {sup 2}B{sub 2} resonance. We focus on the H{sup -} anion fragment, which is produced via dynamics passing through and avoiding the conical intersection with the lower A{sub 1} state, leading to OH ({sup 2}{Pi} ) and OH ({sup 2}{Sigma} ), respectively. The momentum imaging technique, when combined with theoretical calculations on the attachment amplitude and dissociation dynamics, demonstrates that the angular distributions provide a signature of the location of the conical intersection in the space of nuclear configurations.

  10. Dissociations of the night: individual differences in sleep-related experiences and their relation to dissociation and schizotypy.

    PubMed

    Watson, D

    2001-11-01

    The author examined the associations among sleep-related experiences (e.g., hypnagogic hallucinations, nightmares, waking dreams, and lucid dreams), dissociation, schizotypy, and the Big Five personality traits in 2 large student samples. Confirmatory factor analyses indicated that (a) dissociation and schizotypy are strongly correlated-yet distinguishable-constructs, and (b) the differentiation between them can be enhanced by eliminating detachment/depersonalization items from the dissociation scales. A general measure of sleep experiences was substantially correlated with both schizotypy and dissociation (especially the latter) and more weakly related to the Big Five. In contrast, an index of lucid dreaming was weakly related to all of these other scales. These results suggest that measures of dissociation, schizotypy, and sleep-related experiences all define a common domain characterized by unusual cognitions and perceptions. PMID:11727942

  11. Dissociations of the night: individual differences in sleep-related experiences and their relation to dissociation and schizotypy.

    PubMed

    Watson, D

    2001-11-01

    The author examined the associations among sleep-related experiences (e.g., hypnagogic hallucinations, nightmares, waking dreams, and lucid dreams), dissociation, schizotypy, and the Big Five personality traits in 2 large student samples. Confirmatory factor analyses indicated that (a) dissociation and schizotypy are strongly correlated-yet distinguishable-constructs, and (b) the differentiation between them can be enhanced by eliminating detachment/depersonalization items from the dissociation scales. A general measure of sleep experiences was substantially correlated with both schizotypy and dissociation (especially the latter) and more weakly related to the Big Five. In contrast, an index of lucid dreaming was weakly related to all of these other scales. These results suggest that measures of dissociation, schizotypy, and sleep-related experiences all define a common domain characterized by unusual cognitions and perceptions.

  12. DISSOCIATION OF 70S RIBOSOMES: SOME PROPERTIES OF THE DISSOCIATING FACTOR FROM Bacillus stearothermophilus AND Escherichia coli*

    PubMed Central

    Bade, Ernesto G.; González, Nelida S.; Algranati, Israel D.

    1969-01-01

    A protein factor which produces in vitro dissociation of 70S particles into 30S and 50S subunits has been obtained from Bacillus stearothermophilus and Escherichia coli. The factor could be extracted from ribosomes, polyribosomes, and S100 supernatant. The kinetics and temperature curve of the dissociation process in the B. stearothermophilus system have been studied and compared with the reaction in the E. coli system. No species specificity was observed when hybrid mixtures of ribosomes and dissociating factor from both bacteria were used. The wide variations of dissociating activity in cells at different stages of growth and the capacity of the liberated subunits to carry out polypeptide synthesis suggest that the dissociating factor has a physiological role. PMID:4901704

  13. A comparison of energy-resolved vibrational activation/dissociation characteristics of protonated and sodiated high mannose N-glycopeptides.

    PubMed

    Aboufazeli, Forouzan; Kolli, Venkata; Dodds, Eric D

    2015-04-01

    Fragmentation of glycopeptides in tandem mass spectrometry (MS/MS) plays a pivotal role in site-specific protein glycosylation profiling by allowing specific oligosaccharide compositions and connectivities to be associated with specific loci on the corresponding protein. Although MS/MS analysis of glycopeptides has been successfully performed using a number of distinct ion dissociation methods, relatively little is known regarding the fragmentation characteristics of glycopeptide ions with various charge carriers. In this study, energy-resolved vibrational activation/dissociation was examined via collision-induced dissociation for a group of related high mannose tryptic glycopeptides as their doubly protonated, doubly sodiated, and hybrid protonated sodium adduct ions. The doubly protonated glycopeptide ions with various compositions were found to undergo fragmentation over a relatively low but wide range of collision energies compared with the doubly sodiated and hybrid charged ions, and were found to yield both glycan and peptide fragmentation depending on the applied collision energy. By contrast, the various doubly sodiated glycopeptides were found to dissociate over a significantly higher but narrow range of collision energies, and exhibited only glycan cleavages. Interestingly, the hybrid protonated sodium adduct ions were consistently the most stable of the precursor ions studied, and provided fragmentation information spanning both the glycan and the peptide moieties. Taken together, these findings illustrate the influence of charge carrier over the energy-resolved vibrational activation/dissociation characteristics of glycopeptides, and serve to suggest potential strategies that exploit the analytically useful features uniquely afforded by specific charge carriers or combinations thereof.

  14. Characterization and Modeling of the Collision Induced Dissociation Patterns of Deprotonated Glycosphingolipids: Cleavage of the Glycosidic Bond

    NASA Astrophysics Data System (ADS)

    Rožman, Marko

    2016-01-01

    Glycosphingolipid fragmentation behavior was investigated by combining results from analysis of a series of negative ion tandem mass spectra and molecular modeling. Fragmentation patterns extracted from 75 tandem mass spectra of mainly acidic glycosphingolipid species (gangliosides) suggest prominent cleavage of the glycosidic bonds with retention of the glycosidic oxygen atom by the species formed from the reducing end (B and Y ion formation). Dominant product ions arise from dissociation of sialic acids glycosidic bonds whereas product ions resulting from cleavage of other glycosidic bonds are less abundant. Potential energy surfaces and unimolecular reaction rates of several low-energy fragmentation pathways leading to cleavage of glycosidic bonds were estimated in order to explain observed dissociation patterns. Glycosidic bond cleavage in both neutral (unsubstituted glycosyl group) and acidic glycosphingolipids was the outcome of the charge-directed intramolecular nucleophilic substitution (SN2) mechanism. According to the suggested mechanism, the nucleophile in a form of carboxylate or oxyanion attacks the carbon at position one of the sugar ring, simultaneously breaking the glycosidic bond and yielding an epoxide. For gangliosides, unimolecular reaction rates suggest that dominant product ions related to the cleavage of sialic acid glycosidic bonds are formed via direct dissociation channels. On the other hand, low abundant product ions related to the dissociation of other glycosidic bonds are more likely to be the result of sequential dissociation. Although results from this study mainly contribute to the understanding of glycosphingolipid fragmentation chemistry, some mechanistic findings regarding cleavage of the glycosidic bond may be applicable to other glycoconjugates.

  15. Does Nitric Acid Dissociate at the Aqueous Solution Surface?

    SciTech Connect

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-11-03

    Nitric acid is a prevalent component of atmospheric aerosols, and the extent of nitric acid dissociation at aqueous interfaces is relevant to its role in heterogeneous atmospheric chemistry. Several experimental and theoretical studies have suggested that the extent of dissociation of nitric acid near aqueous interfaces is less than in bulk solution. Here, dissociation of HNO3 at the surface of aqueous nitric acid is quantified using X-ray photoelectron spectroscopy of the nitrogen local electronic structure. The relative amounts of undissociated HNO3(aq) and dissociated NO3-(aq) are identified by the distinguishable N1s core-level photoelectron spectra of the two species, and we determine the degree of dissociation, αint, in the interface (the first ~3 layers of solution) as a function of HNO3 concentration. Our measurements show that dissociation is decreased by approximately 20% near the solution interface compared with bulk, and furthermore that dissociation occurs even in the top-most solution layer. The experimental results are supported by first-principles MD simulations, which show that hydrogen-bonds between HNO3 and water molecules at the solution surface stabilize the molecular form at low concentration, in analogy to the stabilization of molecular HNO3 that occurs in bulk solution at high concentration. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  16. Dissociative identity disorder: adaptive deception of self and others.

    PubMed

    Beahrs, J O

    1994-01-01

    Dissociative identity disorder (multiple personality) is increasingly diagnosed, often follows childhood trauma, and is characterized by rigidification of phenomena that resemble hypnosis. To interpret dissociated aspects of selfhood as autonomous entities is a useful heuristic; but when taken too literally, it leads to three kinds of anomaly: (1) legal: dissociators remain culpable for misdeeds carried out beyond apparent awareness or control; (2) clinical: legitimization sometimes leads not to relief, but to escalating cycles of regressive dependency; and (3) scientific: the form of dissociated entities varies with how they are defined, in ways that are intrinsically motivated and clinically manipulable. These anomalies yield to an evolutionary perspective that views dissociative identity disorder as an evolved strategy of adaptive deception of self and others; e.g., a beaten subordinate avoids further retribution by "pleading illness." Such a deceit best avoids detection when fully experienced; through its intensity and persistence, it becomes real at a new level. One's basic competencies remain intact, however, and are the source of the anomalies described. They can be clinically accessed and empowered, providing the key to therapeutic change when dissociative processes are problematic. Overall, despite clear impairment in subjective awareness and volition, dissociative-disordered individuals are best held fully accountable for the consequences of their actions.

  17. The Role of Anxiety and Dissociation in Young Australian Gamblers.

    PubMed

    Cartmill, Tomas; Slatter, Tilsa; Wilkie, Brian

    2015-12-01

    The aim of the present study was to examine predictors of 'escape style' problem gambling among young Australian gamblers. Anxiety and dissociation are considered to be predictors of 'escape style' gambling behaviour although this assessment has neglected consideration of different modes of gambling. This study builds on existing research, to examine the role of anxiety and dissociation in the gambling habits of young Australian male and female gamblers. One hundred and forty-two participants aged between 18 and 35 years self-selected and completed an online questionnaire. The hypothesis that gamblers would have similar levels of dissociation and anxiety despite different modes of gambling was supported. The hypothesis that anxiety and dissociation would both together and uniquely predict problem gambling behaviour across a range of gambling modalities was supported. Further, the hypothesis that there would be an interaction effect between anxiety and dissociation such that their presence together would predict a higher degree of problem gambling behaviour was supported. Results suggest that anxiety and dissociation play an important role in 'escape style' gambling and that strategies to combat problem gambling may benefit from research targeting anxiety and attempting to rechannel dissociative behaviour into healthier pursuits. PMID:25371033

  18. Calculated vibrational states of ozone up to dissociation

    NASA Astrophysics Data System (ADS)

    Ndengué, Steve; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Sun, Zhigang; Guo, Hua

    2016-02-01

    A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. Here we present global "three-well" calculations of all bound vibrational states of three isotopic combinations of ozone (48O3, 16O218O, 16O217O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.

  19. Surface-Induced Dissociation of Peptide Ions: Kinetics and Dynamics

    SciTech Connect

    Laskin, Julia; Futrell, Jean H.; Shukla, Anil K.

    2003-12-01

    Kinetics and dynamics studies have been carried out for the surface-induced dissociation (SID) of a set of model peptides utilizing a specially designed electrospray ionization Fourier Transform ion cyclotron resonance mass spectrometer in which mass-selected and vibrationally relaxed ions are collided on a orthogonally-mounted fluorinated self-assembled monolayer on Au{l_brace}111{r_brace} crystal. The sampling time in this apparatus can be varied from hundreds of microseconds to tens of seconds, enabling the investigation of kinetics of ion decomposition over an extended range of decomposition rates. RRKM-based modeling of these reactions for a set of polyalanines demonstrates that SID kinetics of these simple peptides is very similar to slow, multiple-collision activation and that the distribution of internal energies following collisional activation is indistinguishable from a thermal distribution. For more complex peptides comprised of several amino acids and with internal degrees of freedom ( DOF) of the order of 350 there is a dramatic change in kinetics in which RRKM kinetics is no longer capable of describing the decomposition of these complex ions. A combination of RRKM kinetics and the sudden death approximation, according to which decomposition occurs instantaneously, is a satisfactory description. This implies that a population of ions-which is dependant on the nature of the peptide, kinetic energy and sampling time-decomposes on or very near the surface. The shattering transition is described quantitatively for the limited set of molecules examined to date

  20. Surface-Induced Dissociation of Peptide Ions: Kinetics and Dynamics

    SciTech Connect

    Laskin, Julia; Futrell, Jean H.

    2003-12-01

    Kinetics and dynamics studies have been carried out for the surface-induced dissociation (SID) of a set of model peptides utilizing a specially designed electro spray ionization Fourier Transform Ion cyclotron resonance mass spectrometer in which mass-selected and vibrationally relaxed ions are collided on an orthogonally-mounted fluorinated self-assembled monolayer on Au {111} crystal. The sampling time in this apparatus can be varied from hundreds of microseconds to tens of seconds, enabling the investigation of kinetics of ion decomposition over an extended range of decomposition rates. RRKM-based modeling of these reactions for a set of polyalanines demonstrates that kinetics of these simple peptides is very similar to slow, multiple-collision activation and that the distribution of internal energies following collisional activation is indistinguishable from a thermal distribution. For more complex peptides comprised of several amino acids and with internal degrees of freedom (DOF) of the order of 350 there is a dramatic change in kinetics in which RRKM kinetics is no longer capable of describing the decomposition of these complex ions. A combination of RRKM kinetics and the “sudden death” approximation, according to which decomposition occurs instantaneously, is a satisfactory description. This implies that a population of ions – which is dependant on the nature of the peptide, kinetic energy and sampling time – decomposes on or very near the surface. The shattering transition is described quantitatively for the limited set of molecules examined to date.

  1. Evolution of PAHs in PhotoDissociation Regions

    NASA Astrophysics Data System (ADS)

    Tielens, Alexander

    2015-10-01

    Interstellar Polycyclic Aromatic Hydrocarbons (PAHs) are an important component of the interstellar medium (ISM). Observations have shown that the characteristics of PAHs (sizes, abundances) vary in PhotoDissociation Regions (PDRs), likely reflecting processing by the strong UV radiation field. We propose to measure the variation of the PAH size and abundance as a function of the physical conditions in the PDRs associated with the larger Orion Nebula and the reflection nebula, NGC 2023. These two nebulae have been extensively studied and the physical conditions (incident radiation field and density) have been well characterized and are known to vary with position. We will image these nebulae in the 3.3 and 11.2 micron PAH features using FLITECAM and FORCAST. The large field of view and the good sensitivity of these two instruments make this program unique to SOFIA. Both bands are CH modes (stretching and out-of-plane bending) and originate in neutral PAHs. The ratio of these two bands is a good measure of the size of the emitting PAHs. In this way, we can trace the variation in the PAH size. Combining the SOFIA data with Spitzer/IRAC and Herschel/PACS data, we can determine the integrated intensity of the PAH bands relative to the dust emission, which is a direct measure of the PAH-to-dust ratio. We can then relate the PAH size and abundance to the local physical conditions, and determine the role of top-down chemistry in the chemical composition of PDRs.

  2. Calculated vibrational states of ozone up to dissociation.

    PubMed

    Ndengué, Steve; Dawes, Richard; Wang, Xiao-Gang; Carrington, Tucker; Sun, Zhigang; Guo, Hua

    2016-02-21

    A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. Here we present global "three-well" calculations of all bound vibrational states of three isotopic combinations of ozone ((48)O3, (16)O2 (18)O, (16)O2 (17)O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.

  3. Errors of logic and scholarship concerning dissociative identity disorder.

    PubMed

    Ross, Colin A

    2009-01-01

    The author reviewed a two-part critique of dissociative identity disorder published in the Canadian Journal of Psychiatry. The two papers contain errors of logic and scholarship. Contrary to the conclusions in the critique, dissociative identity disorder has established diagnostic reliability and concurrent validity, the trauma histories of affected individuals can be corroborated, and the existing prospective treatment outcome literature demonstrates improvement in individuals receiving psychotherapy for the disorder. The available evidence supports the inclusion of dissociative identity disorder in future editions of the Diagnostic and Statistical Manual of Mental Disorders.

  4. General features of the dissociative recombination of polyatomic molecules

    DOE PAGES

    Pratt, S. T.; Jungen, Ch.; Schneider, I. F.; Dulieu, O.; Robert, J.

    2015-01-29

    We discuss some aspects of a simple expression for the low-energy dissociative recombination cross section that applies when the recombination process is dominated by the indirect mechanism. In most previous applications, this expression has been applied to capture into vibrationally excited Rydberg states with the assumption that capture is always followed by prompt dissociation. Here we consider the dissociative recombination of larger polyatomic ions and electrons. More specifically, we consider capture into electronically core-excited Rydberg states, and begin to assess its potential importance for larger systems.

  5. The unification of consciousness: Approaches to the healing of dissociation.

    PubMed

    Rosik, C H

    1995-09-01

    This study examines the process of unifying consciousness as described in the Christian mystical tradition and in the psychological treatment of dissociative identity disorder (DID). A comparison of the experience of the self in the contemplative and the DID patient is also undertaken to emphasize points of continuity. The present analysis proposes that differentiating first-order dissociation (separation from a divine being or source) from second-order dissociation (separation from parts of one's own self and experiences) can preserve the insights gathered from both spiritual and psychological perspectives.

  6. Clinical phenomenology of child and adolescent dissociative disorders.

    PubMed

    Hornstein, N L; Putnam, F W

    1992-11-01

    A comparison of two separately diagnosed samples of children and adolescents with dissociative disorders demonstrates good construct validity for these diagnoses in childhood. Descriptive analyses of the total sample reveal a clinical profile characterized by a plethora of affective, anxiety, conduct, posttraumatic, and dissociative symptoms. Children with multiple personality disorder (MPD) differ from those with dissociative disorder not otherwise specified (DDNOS) in having more amnesias, identity disturbances, and hallucinations. Adolescents were more symptomatic than children age 11 or younger and more likely to receive a diagnosis of multiple personality disorder.

  7. [Introducing treatment for dissociative identity disorder].

    PubMed

    Kitamura, Naoto

    2011-01-01

    This paper is a case presentation and study of the introduction of treatment for Dissociative Identity Disorder (DID). Since one manifestation of the pathology of DID is that sufferers avoid relying on others, at the start of treatment we try to stabilise the relationship between clinicians and patients; that is to say, we aim to build a treatment relationship which will be able to gradually overcome the patients' dread of relying on clinicians. In parallel with this we undertake a thorough psychiatric assessment of their condition. This is a standard treatment plan, which follows the general principles of clinical psychiatry. On the other hand, the specialist aspect of DID treatment calls for handling the unique behaviours of a group of mutually opposed alternating personalities appropriately, while always paying consistent attention to the traumatic memories which are connected to the formation and maintenance of the condition. This paper presents the first DID case which the author has taken charge of. There were some difficulties in the early stages of treatment, but after modifying some parts to acknowledge the alternating personalities as independent personalities in face-to-face interviews and psychological education for families, the stabilisation of the treatment structure progressed gradually and the stability of the relationship between clinicians and patients itself has become the focus.

  8. Visuomotor Dissociation in Cerebral Scaling of Size.

    PubMed

    Potgieser, Adriaan R E; de Jong, Bauke M

    2016-01-01

    Estimating size and distance is crucial in effective visuomotor control. The concept of an internal coordinate system implies that visual and motor size parameters are scaled onto a common template. To dissociate perceptual and motor components in such scaling, we performed an fMRI experiment in which 16 right-handed subjects copied geometric figures while the result of drawing remained out of sight. Either the size of the example figure varied while maintaining a constant size of drawing (visual incongruity) or the size of the examples remained constant while subjects were instructed to make changes in size (motor incongruity). These incongruent were compared to congruent conditions. Statistical Parametric Mapping (SPM8) revealed brain activations related to size incongruity in the dorsolateral prefrontal and inferior parietal cortex, pre-SMA / anterior cingulate and anterior insula, dominant in the right hemisphere. This pattern represented simultaneous use of a 'resized' virtual template and actual picture information requiring spatial working memory, early-stage attention shifting and inhibitory control. Activations were strongest in motor incongruity while right pre-dorsal premotor activation specifically occurred in this condition. Visual incongruity additionally relied on a ventral visual pathway. Left ventral premotor activation occurred in all variably sized drawing while constant visuomotor size, compared to congruent size variation, uniquely activated the lateral occipital cortex additional to superior parietal regions. These results highlight size as a fundamental parameter in both general hand movement and movement guided by objects perceived in the context of surrounding 3D space. PMID:26963705

  9. Activated Dissociation of HCl on Au(111).

    PubMed

    Shirhatti, Pranav R; Geweke, Jan; Steinsiek, Christoph; Bartels, Christof; Rahinov, Igor; Auerbach, Daniel J; Wodtke, Alec M

    2016-04-01

    We report zero-coverage reaction probabilities (S0) for HCl dissociative adsorption on Au(111) obtained by the seeded molecular beam hot-nozzle method. For measurements at normal incidence with mean translational energies ranging from 0.94 to 2.56 eV (nozzle temperatures 296 to 1060 K), S0 increased from 6 × 10(-6) to 2 × 10(-2). S0 also increased with increasing nozzle temperature for fixed incidence energy associated with the motion normal to the surface. Accounting for the influence of the vibrational state population and translational energy distributions in the incident beam, we are able to compare the experimental results to recent theoretical predictions. These calculations, performed employing 6-D quantum dynamics on an electronically adiabatic potential energy surface obtained using density functional theory at the level of the generalized gradient approximation and the static surface approximation, severely overestimate the reaction probabilities when compared with our experimental results. We discuss some possible reasons for this large disagreement. PMID:26990513

  10. Dissociation of recombinant prion autocatalysis from infectivity.

    PubMed

    Noble, Geoffrey P; Supattapone, Surachai

    2015-01-01

    Within the mammalian prion field, the existence of recombinant prion protein (PrP) conformers with self-replicating (ie. autocatalytic) activity in vitro but little to no infectious activity in vivo challenges a key prediction of the protein-only hypothesis of prion replication--that autocatalytic PrP conformers should be infectious. To understand this dissociation of autocatalysis from infectivity, we recently performed a structural and functional comparison between a highly infectious and non-infectious pair of autocatalytic recombinant PrP conformers derived from the same initial prion strain. (1) We identified restricted, C-terminal structural differences between these 2 conformers and provided evidence that these relatively subtle differences prevent the non-infectious conformer from templating the conversion of native PrP(C) substrates containing a glycosylphosphatidylinositol (GPI) anchor. (1) In this article we discuss a model, consistent with these findings, in which recombinant PrP, lacking post-translational modifications and associated folding constraints, is capable of adopting a wide variety of autocatalytic conformations. Only a subset of these recombinant conformers can be adopted by post-translationally modified native PrP(C), and this subset represents the recombinant conformers with high specific infectivity. We examine this model's implications for the generation of highly infectious recombinant prions and the protein-only hypothesis of prion replication.

  11. Infrared Multiphoton Dissociation for Quantitative Shotgun Proteomics

    PubMed Central

    Ledvina, Aaron R.; Lee, M. Violet; McAlister, Graeme C.; Westphall, Michael S.; Coon, Joshua J.

    2012-01-01

    We modified a dual-cell linear ion trap mass spectrometer to perform infrared multiphoton dissociation (IRMPD) in the low pressure trap of a dual-cell quadrupole linear ion trap (dual cell QLT) and perform large-scale IRMPD analyses of complex peptide mixtures. Upon optimization of activation parameters (precursor q-value, irradiation time, and photon flux), IRMPD subtly, but significantly outperforms resonant excitation CAD for peptides identified at a 1% false-discovery rate (FDR) from a yeast tryptic digest (95% confidence, p = 0.019). We further demonstrate that IRMPD is compatible with the analysis of isobaric-tagged peptides. Using fixed QLT RF amplitude allows for the consistent retention of reporter ions, but necessitates the use of variable IRMPD irradiation times, dependent upon precursor mass-to-charge (m/z). We show that IRMPD activation parameters can be tuned to allow for effective peptide identification and quantitation simultaneously. We thus conclude that IRMPD performed in a dual-cell ion trap is an effective option for the large-scale analysis of both unmodified and isobaric-tagged peptides. PMID:22480380

  12. Visuomotor Dissociation in Cerebral Scaling of Size.

    PubMed

    Potgieser, Adriaan R E; de Jong, Bauke M

    2016-01-01

    Estimating size and distance is crucial in effective visuomotor control. The concept of an internal coordinate system implies that visual and motor size parameters are scaled onto a common template. To dissociate perceptual and motor components in such scaling, we performed an fMRI experiment in which 16 right-handed subjects copied geometric figures while the result of drawing remained out of sight. Either the size of the example figure varied while maintaining a constant size of drawing (visual incongruity) or the size of the examples remained constant while subjects were instructed to make changes in size (motor incongruity). These incongruent were compared to congruent conditions. Statistical Parametric Mapping (SPM8) revealed brain activations related to size incongruity in the dorsolateral prefrontal and inferior parietal cortex, pre-SMA / anterior cingulate and anterior insula, dominant in the right hemisphere. This pattern represented simultaneous use of a 'resized' virtual template and actual picture information requiring spatial working memory, early-stage attention shifting and inhibitory control. Activations were strongest in motor incongruity while right pre-dorsal premotor activation specifically occurred in this condition. Visual incongruity additionally relied on a ventral visual pathway. Left ventral premotor activation occurred in all variably sized drawing while constant visuomotor size, compared to congruent size variation, uniquely activated the lateral occipital cortex additional to superior parietal regions. These results highlight size as a fundamental parameter in both general hand movement and movement guided by objects perceived in the context of surrounding 3D space.

  13. Visuomotor Dissociation in Cerebral Scaling of Size

    PubMed Central

    Potgieser, Adriaan R. E.; de Jong, Bauke M.

    2016-01-01

    Estimating size and distance is crucial in effective visuomotor control. The concept of an internal coordinate system implies that visual and motor size parameters are scaled onto a common template. To dissociate perceptual and motor components in such scaling, we performed an fMRI experiment in which 16 right-handed subjects copied geometric figures while the result of drawing remained out of sight. Either the size of the example figure varied while maintaining a constant size of drawing (visual incongruity) or the size of the examples remained constant while subjects were instructed to make changes in size (motor incongruity). These incongruent were compared to congruent conditions. Statistical Parametric Mapping (SPM8) revealed brain activations related to size incongruity in the dorsolateral prefrontal and inferior parietal cortex, pre-SMA / anterior cingulate and anterior insula, dominant in the right hemisphere. This pattern represented simultaneous use of a ‘resized’ virtual template and actual picture information requiring spatial working memory, early-stage attention shifting and inhibitory control. Activations were strongest in motor incongruity while right pre-dorsal premotor activation specifically occurred in this condition. Visual incongruity additionally relied on a ventral visual pathway. Left ventral premotor activation occurred in all variably sized drawing while constant visuomotor size, compared to congruent size variation, uniquely activated the lateral occipital cortex additional to superior parietal regions. These results highlight size as a fundamental parameter in both general hand movement and movement guided by objects perceived in the context of surrounding 3D space. PMID:26963705

  14. Dissociable brain biomarkers of fluid intelligence.

    PubMed

    Paul, Erick J; Larsen, Ryan J; Nikolaidis, Aki; Ward, Nathan; Hillman, Charles H; Cohen, Neal J; Kramer, Arthur F; Barbey, Aron K

    2016-08-15

    Cognitive neuroscience has long sought to understand the biological foundations of human intelligence. Decades of research have revealed that general intelligence is correlated with two brain-based biomarkers: the concentration of the brain biochemical N-acetyl aspartate (NAA) measured by proton magnetic resonance spectroscopy (MRS) and total brain volume measured using structural MR imaging (MRI). However, the relative contribution of these biomarkers in predicting performance on core facets of human intelligence remains to be well characterized. In the present study, we sought to elucidate the role of NAA and brain volume in predicting fluid intelligence (Gf). Three canonical tests of Gf (BOMAT, Number Series, and Letter Sets) and three working memory tasks (Reading, Rotation, and Symmetry span tasks) were administered to a large sample of healthy adults (n=211). We conducted exploratory factor analysis to investigate the factor structure underlying Gf independent from working memory and observed two Gf components (verbal/spatial and quantitative reasoning) and one working memory component. Our findings revealed a dissociation between two brain biomarkers of Gf (controlling for age and sex): NAA concentration correlated with verbal/spatial reasoning, whereas brain volume correlated with quantitative reasoning and working memory. A follow-up analysis revealed that this pattern of findings is observed for males and females when analyzed separately. Our results provide novel evidence that distinct brain biomarkers are associated with specific facets of human intelligence, demonstrating that NAA and brain volume are independent predictors of verbal/spatial and quantitative facets of Gf. PMID:27184204

  15. Memory fragmentation in dissociative identity disorder.

    PubMed

    van der Hart, Onno; Bolt, Hilde; van der Kolk, Bessel A

    2005-01-01

    This study examined the quality of self-reported memories of traumatic experiences in participants with dissociative identity disorder (DID) and compared them with their memories of non-traumatic, but emotionally significant life experiences. Systematic interview data were gathered from 30 DID patients in The Netherlands. All participants reported a history of severe childhood abuse; 93.3% reported some period of amnesia for the index traumatic event, and 33.3% reported periods of amnesia for significant non-traumatic childhood experiences. All participants who had been amnestic for their trauma reported that their memories were initially retrieved in the form of somatosensory flashbacks. This suggests that, like PTSD patients, DID patients at least initially recall their trauma not as a narrative, but as somatosensory re-experiencing. Surprisingly, however, DID participants also recalled emotionally charged non-traumatic life events with significant somatosensory components, a phenomenon that has not been previously reported. This finding raises important issues regarding basic memory processing abnormalities in DID patients.

  16. Dissociative amnesia in dissociative disorders and borderline personality disorder: self-rating assessment in a college population.

    PubMed

    Sar, Vedat; Alioğlu, Firdevs; Akyuz, Gamze; Karabulut, Sercan

    2014-01-01

    Dissociative amnesia (DA) among subjects with a dissociative disorder and/or borderline personality disorder (BPD) recruited from a nonclinical population was examined. The Steinberg Dissociative Amnesia Questionnaire (SDAQ), the Childhood Trauma Questionnaire, and the self-report screening tool of the BPD section of the Structured Clinical Interview for DSM-IV(SCID-BPD) were administered to 1,301 college students. A total of 80 participants who were diagnosed with BPD according to the clinician-administered SCID-BPD and 111 nonborderline controls were evaluated using the Structured Clinical Interview for DSM-IV Dissociative Disorders (SCID-D) by a psychiatrist blind to diagnosis and scale scores. Internal consistency analyses and test-retest evaluations suggested that the SDAQ is a reliable instrument for the population studied. Of the participants, 20.6% reported an SDAQ score of 20 or above and impairment by DA. Those who had both dissociative disorder and BPD (n = 78) had the highest SDAQ scores. Both disorders had significant effects on the SCID-D total and amnesia scores in the variance analysis. On SDAQ scores, however, only BPD had this effect. There was a significant interaction between the 2 disorders for the SCID-D total but not for the SDAQ or SCID-D amnesia scores. BPD represented the severity of dissociation and childhood trauma in this study group. However, in contrast to the dissociative disorders, BPD was characterized by better awareness of DA in self-report. The discrepancies between self-report and clinical interview associated with BPD and dissociative disorders are discussed in the context of betrayal theory (J. J. Freyd, 1994) of BPD and perceptual theory (D. B. Beere, 2009) of dissociative disorders.

  17. Pulsed IR heating studies of single-molecule DNA duplex dissociation kinetics and thermodynamics.

    PubMed

    Holmstrom, Erik D; Dupuis, Nicholas F; Nesbitt, David J

    2014-01-01

    Single-molecule fluorescence spectroscopy is a powerful technique that makes it possible to observe the conformational dynamics associated with biomolecular processes. The addition of precise temperature control to these experiments can yield valuable thermodynamic information about equilibrium and kinetic rate constants. To accomplish this, we have developed a microscopy technique based on infrared laser overtone/combination band absorption to heat small (≈10(-11) liter) volumes of water. Detailed experimental characterization of this technique reveals three major advantages over conventional stage heating methods: 1), a larger range of steady-state temperatures (20-100°C); 2), substantially superior spatial (≤20 μm) control; and 3), substantially superior temporal (≈1 ms) control. The flexibility and breadth of this spatial and temporally resolved laser-heating approach is demonstrated in single-molecule fluorescence assays designed to probe the dissociation of a 21 bp DNA duplex. These studies are used to support a kinetic model based on nucleic acid end fraying that describes dissociation for both short (<10 bp) and long (>10 bp) DNA duplexes. These measurements have been extended to explore temperature-dependent kinetics for the 21 bp construct, which permit determination of single-molecule activation enthalpies and entropies for DNA duplex dissociation.

  18. Pulsed IR Heating Studies of Single-Molecule DNA Duplex Dissociation Kinetics and Thermodynamics

    PubMed Central

    Holmstrom, Erik D.; Dupuis, Nicholas F.; Nesbitt, David J.

    2014-01-01

    Single-molecule fluorescence spectroscopy is a powerful technique that makes it possible to observe the conformational dynamics associated with biomolecular processes. The addition of precise temperature control to these experiments can yield valuable thermodynamic information about equilibrium and kinetic rate constants. To accomplish this, we have developed a microscopy technique based on infrared laser overtone/combination band absorption to heat small (≈10−11 liter) volumes of water. Detailed experimental characterization of this technique reveals three major advantages over conventional stage heating methods: 1), a larger range of steady-state temperatures (20–100°C); 2), substantially superior spatial (≤20 μm) control; and 3), substantially superior temporal (≈1 ms) control. The flexibility and breadth of this spatial and temporally resolved laser-heating approach is demonstrated in single-molecule fluorescence assays designed to probe the dissociation of a 21 bp DNA duplex. These studies are used to support a kinetic model based on nucleic acid end fraying that describes dissociation for both short (<10 bp) and long (>10 bp) DNA duplexes. These measurements have been extended to explore temperature-dependent kinetics for the 21 bp construct, which permit determination of single-molecule activation enthalpies and entropies for DNA duplex dissociation. PMID:24411254

  19. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOEpatents

    Smith, L.A. Jr.; Jones, E.M. Jr.; Hearn, D.

    1984-05-08

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

  20. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOEpatents

    Smith, Jr., Lawrence A.; Jones, Jr., Edward M.; Hearn, Dennis

    1984-01-01

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150.degree. to 250.degree. F. at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C.sub.3 to C.sub.6 and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom.

  1. Associations of emotional arousal, dissociation and symptom severity with operant conditioning in borderline personality disorder.

    PubMed

    Paret, Christian; Hoesterey, Steffen; Kleindienst, Nikolaus; Schmahl, Christian

    2016-10-30

    Those with borderline personality disorder (BPD) display altered evaluations regarding reward and punishment compared to others. The processing of rewards is basal for operant conditioning. However, studies addressing operant conditioning in BPD patients are rare. In the current study, an operant conditioning task combining learning acquisition and reversal was used. BPD patients and matched healthy controls (HCs) were exposed to aversive and neutral stimuli to assess the influence of emotion on learning. Picture content, dissociation, aversive tension and symptom severity were rated. Error rates were measured. Results showed no group interactions between aversive versus neutral scenes. The higher emotional arousal, dissociation and tension, the worse the acquisition, but not reversal, scores were for BPD patients. Scores from the Borderline Symptom List were associated with more errors in the reversal, but not the acquisition phase. The results are preliminary evidence for impaired acquisition learning due to increased emotional arousal, dissociation and tension in BPD patients. A failure to process punishment in the reversal phase was associated with symptom severity and may be related to neuropsychological dysfunctioning involving the ventromedial prefrontal cortex. Conclusions are limited due to the correlational study design and the small sample size. PMID:27491014

  2. Associations of emotional arousal, dissociation and symptom severity with operant conditioning in borderline personality disorder.

    PubMed

    Paret, Christian; Hoesterey, Steffen; Kleindienst, Nikolaus; Schmahl, Christian

    2016-10-30

    Those with borderline personality disorder (BPD) display altered evaluations regarding reward and punishment compared to others. The processing of rewards is basal for operant conditioning. However, studies addressing operant conditioning in BPD patients are rare. In the current study, an operant conditioning task combining learning acquisition and reversal was used. BPD patients and matched healthy controls (HCs) were exposed to aversive and neutral stimuli to assess the influence of emotion on learning. Picture content, dissociation, aversive tension and symptom severity were rated. Error rates were measured. Results showed no group interactions between aversive versus neutral scenes. The higher emotional arousal, dissociation and tension, the worse the acquisition, but not reversal, scores were for BPD patients. Scores from the Borderline Symptom List were associated with more errors in the reversal, but not the acquisition phase. The results are preliminary evidence for impaired acquisition learning due to increased emotional arousal, dissociation and tension in BPD patients. A failure to process punishment in the reversal phase was associated with symptom severity and may be related to neuropsychological dysfunctioning involving the ventromedial prefrontal cortex. Conclusions are limited due to the correlational study design and the small sample size.

  3. Negligible Isotopic Effect on Dissociation of Hydrogen Bonds.

    PubMed

    Ge, Chuanqi; Shen, Yuneng; Deng, Gang-Hua; Tian, Yuhuan; Yu, Dongqi; Yang, Xueming; Yuan, Kaijun; Zheng, Junrong

    2016-03-31

    Isotopic effects on the formation and dissociation kinetics of hydrogen bonds are studied in real time with ultrafast chemical exchange spectroscopy. The dissociation time of hydrogen bond between phenol-OH and p-xylene (or mesitylene) is found to be identical to that between phenol-OD and p-xylene (or mesitylene) in the same solvents. The experimental results demonstrate that the isotope substitution (D for H) has negligible effects on the hydrogen bond kinetics. DFT calculations show that the isotope substitution does not significantly change the frequencies of vibrational modes that may be along the hydrogen bond formation and dissociation coordinate. The zero point energy differences of these modes between hydrogen bonds with OH and OD are too small to affect the activation energy of the hydrogen bond dissociation in a detectible way at room temperature.

  4. Memories of attachment hamper EEG cortical connectivity in dissociative patients.

    PubMed

    Farina, Benedetto; Speranza, Anna Maria; Dittoni, Serena; Gnoni, Valentina; Trentini, Cristina; Vergano, Carola Maggiora; Liotti, Giovanni; Brunetti, Riccardo; Testani, Elisa; Della Marca, Giacomo

    2014-08-01

    In this study, we evaluated cortical connectivity modifications by electroencephalography (EEG) lagged coherence analysis, in subjects with dissociative disorders and in controls, after retrieval of attachment memories. We asked thirteen patients with dissociative disorders and thirteen age- and sex-matched healthy controls to retrieve personal attachment-related autobiographical memories through adult attachment interviews (AAI). EEG was recorded in the closed eyes resting state before and after the AAI. EEG lagged coherence before and after AAI was compared in all subjects. In the control group, memories of attachment promoted a widespread increase in EEG connectivity, in particular in the high-frequency EEG bands. Compared to controls, dissociative patients did not show an increase in EEG connectivity after the AAI. Conclusions: These results shed light on the neurophysiology of the disintegrative effect of retrieval of traumatic attachment memories in dissociative patients.

  5. Frustration and fulfillment of needs in dissociative and conversion disorders.

    PubMed

    Ishikura, Reiji; Tashiro, Nobutada

    2002-08-01

    We reviewed all patients with dissociative disorders (nine patients with dissociative amnesia or dissociative fugue) and conversion disorders (10 patients) who were admitted and treated during the past 15 years. Needs frustrated at the appearance of the symptoms and those fulfilled at discharge were studied in both groups using Maslow's hierarchy of needs. The patients of both groups who encountered troubles in their life events were found to have frustrated needs. These symptoms tended to be accompanied more often by frustrations regarding a 'need for love' in the dissociative disorders group and by frustration in the need for 'self-esteem and self-actualization' in the conversion disorders group. In addition, needs of lower orders were already threatened at onset in many patients. The symptoms disappeared in patients in whom the situation completely improved (needs were fulfilled), but the symptoms were alleviated or unchanged in those in whom the problems remained unresolved.

  6. Child sexual abuse survivors with dissociative amnesia: what's the difference?

    PubMed

    Wolf, Molly R; Nochajski, Thomas H

    2013-01-01

    Although the issue of dissociative amnesia in adult survivors of child sexual abuse has been contentious, many research studies have shown that there is a subset of child sexual abuse survivors who have forgotten their abuse and later remembered it. Child sexual abuse survivors with dissociative amnesia histories have different formative and therapeutic issues than survivors of child sexual abuse who have had continuous memory of their abuse. This article first discusses those differences in terms of the moderating risk factors for developing dissociative amnesia (e.g., age, ethnicity, gender, etc.) and then mediating risk factors (e.g., social support, trait dissociativity, etc.). The differences between the two types of survivors are then explored in terms of treatment issues.

  7. Catalytic efficiency of Nb and Nb oxides for hydrogen dissociation

    SciTech Connect

    Isobe, Shigehito; Kudoh, Katsuhiro; Hino, Satoshi; Hashimoto, Naoyuki; Ohnuki, Somei; Hara, Kenji

    2015-08-24

    In this letter, catalytic efficiency of Nb, NbO, Nb{sub 2}O{sub 3}, NbO{sub 2}, and Nb{sub 2}O{sub 5} for dissociation and recombination of hydrogen were experimentally investigated. On the surface of Nb and Nb oxides in a gas mixture of H{sub 2} and D{sub 2}, H{sub 2} and D{sub 2} molecules can be dissociated to H and D atoms; then, H{sub 2}, D{sub 2}, and HD molecules can be produced according to the law of probability. With increase of frequency of the dissociation and recombination, HD ratio increases. The ratio of H{sub 2} and HD gas was analyzed by quadrupole mass spectrometry. As a result, NbO showed the highest catalytic activity towards hydrogen dissociation and recombination.

  8. Communication: Enhanced dissociative chemisorption of CO2 via vibrational excitation

    NASA Astrophysics Data System (ADS)

    Jiang, Bin; Guo, Hua

    2016-03-01

    A fully coupled global nine-dimensional potential energy surface for the dissociative chemisorption of CO2 on Ni(100) is constructed from ˜18 000 density functional points. It reveals a complex reaction pathway dominated by two near iso-energetic transition states. The dissociation probabilities obtained by quasi-classical trajectories on the potential energy surface reproduced experimental trends, and indicate that vibrational excitations of CO2 significantly promote the dissociation. Using the sudden vector projection model, the behavior of the reactivity is rationalized by couplings with the reaction coordinate at each transition state. These results offer plausible rationalization for the observed enhancement of CO2 dissociation in non-thermal plasmas by metal surfaces.

  9. Cognitive therapy of dissociative symptoms associated with trauma.

    PubMed

    Kennerley, H

    1996-09-01

    The presentation of dissociative symptoms is not uncommon in clinical settings, particularly when the client has suffered trauma. The phenomenon of dissociation ranges from benign incidents, such as daydreaming, to potentially life-threatening experiences when it precipitates self-harm. Its presentation may be subtle, belying the distress which it can provoke. Cognitive therapists are well equipped to help clients formulate a working conceptualization of the dissociative episode and to develop a range of coping skills to manage and overcome the experience. This paper discusses practical ways in which the cognitive therapist can use standard and schema-focused cognitive therapy to help clients to better deal with the distressing aspects of dissociation.

  10. [Persistent Perpetrator Contact in a Patient with Dissociative Identity Disorder].

    PubMed

    Tschöke, Stefan; Eisele, Frank; Steinert, Tilman

    2016-05-01

    The case of a young woman with still ongoing incest and forced prostitution is presented. The criteria for a dissociative identity disorder (DID) were met. Due to persistent contact to the perpetrator she was repeatedly revictimized. Based on the model of trauma-related dissociation we discuss to what extent she was capable of self-determined decision making as well as therapeutic consequences resulting therefrom. PMID:26556682

  11. [Persistent Perpetrator Contact in a Patient with Dissociative Identity Disorder].

    PubMed

    Tschöke, Stefan; Eisele, Frank; Steinert, Tilman

    2016-05-01

    The case of a young woman with still ongoing incest and forced prostitution is presented. The criteria for a dissociative identity disorder (DID) were met. Due to persistent contact to the perpetrator she was repeatedly revictimized. Based on the model of trauma-related dissociation we discuss to what extent she was capable of self-determined decision making as well as therapeutic consequences resulting therefrom.

  12. Modeling dissociation of hydrate bearing sediments under shear

    NASA Astrophysics Data System (ADS)

    Lin, J. S.; Choi, J. H.; Seol, Y.; Rutqvist, J.

    2015-12-01

    To assess the stability of ground during gas production from hydrate bearing sediments, it is of fundamental importance that the constitutive model employed and the computational procedure adopted are capable and accurate. One way to establish credence is to investigate if observation from laboratory tests could be reproduced in analysis. From this consideration, this study modeled laboratory triaxial tests in which hydrate dissociation was induced when a certain level of shear stress was reached. During the dissociation, however, both the axial and the confining stresses were kept unchanged. There were basically two scenarios observed: If the applied shear stress was higher than the shear strength of the hydrate free host soil, failure would take place during the dissociation; otherwise the sample would remain stable. The dissociation was induced either by a temperature raise or through pore pressure reduction. To model such tests, a coupled procedure was employed: the geomechanical analysis was conducted in FLAC3D, and the multiphase flow was conducted in TOUGH+. In this study, an SMP critical state constitutive model was implemented in the FLAC3D. This study successfully reproduced the observation from the laboratory tests. It showed that if the dissociation was caused by temperature change alone, failure would take place during dissociation. On the other hand, the modeling results also showed that if the dissociation was induced by pressure reduction, a sample could remain stable during dissociation because the effective confining stress was raised, but it would fail afterwards when the pre-association fluid pressure was allowed to return and the pace of hydrate reformation lagged behind.

  13. LOVTRAP: an optogenetic system for photoinduced protein dissociation.

    PubMed

    Wang, Hui; Vilela, Marco; Winkler, Andreas; Tarnawski, Miroslaw; Schlichting, Ilme; Yumerefendi, Hayretin; Kuhlman, Brian; Liu, Rihe; Danuser, Gaudenz; Hahn, Klaus M

    2016-09-01

    LOVTRAP is an optogenetic approach for reversible light-induced protein dissociation using protein A fragments that bind to the LOV domain only in the dark, with tunable kinetics and a >150-fold change in the dissociation constant (Kd). By reversibly sequestering proteins at mitochondria, we precisely modulated the proteins' access to the cell edge, demonstrating a naturally occurring 3-mHz cell-edge oscillation driven by interactions of Vav2, Rac1, and PI3K proteins. PMID:27427858

  14. Energetics from Slow Infrared Multiphoton Dissociation of Biomolecules

    PubMed Central

    Jockusch, Rebecca A.; Paech, Kolja

    2005-01-01

    Photodissociation kinetics of the protonated pentapeptide leucine enkephalin measured using a cw CO2 laser and a Fourier-transform mass spectrometer are reported. A short induction period, corresponding to the time required to raise the internal energy of the ion population to a (dissociating) steady state, is observed. After this induction period, the dissociation data are accurately fit by first-order kinetics. A plot of the log of the unimolecular dissociation rate constant, kuni, as a function of the log of laser power is linear at low laser powers (<9 W, kuni <0.05 s−1), but tapers off at high laser power (9–33 W, kuni = 0.05–7 s−1). The entire measured dissociation curve can be accurately fit by an exponential function plus a constant. The experiment is simulated using a master equation formalism. In the model, the laser radiation is described as an energetically flat-topped distribution which is spatially uniform. This description is consistent with experimental results which indicate that ion motion within the cell averages out spatial inhomogeneities in the laser light. The model has several adjustable parameters. The effect of varying these parameters on the calculated kinetics and power dependence curves is discussed. A procedure for determining a limited range of threshold dissociation energy, Eo, which fits both the measured induction period and power dependence curves, is presented. Using this procedure, Eo of leucine enkephalin is determined to be 1.12–1.46 eV. This result is consistent with, although less precise than, values measured previously using blackbody infrared radiative dissociation. Although the blackbody dissociation results were used as a starting point to search for fits of the master equation model to experiment, these results demonstrate that it is, in principle, possible to determine a limited range of Eo from slow infrared multiphoton dissociation data alone. PMID:16467893

  15. Dissociative disorder due to Graves' hyperthyroidism: a case report.

    PubMed

    Mizutani, Kaoru; Nishimura, Katsuji; Ichihara, Atsuhiro; Ishigooka, Jun

    2014-01-01

    We report the case of a 20-year-old Japanese woman with no psychiatric history with apparent dissociative symptoms. These consisted of amnesia for episodes of shoplifting behaviors and a suicide attempt, developing together with an exacerbation of Graves' hyperthyroidism. Patients with Graves' disease frequently manifest various psychiatric disorders; however, very few reports have described dissociative disorder due to this disease. Along with other possible causes, for example, encephalopathy associated with autoimmune thyroid disease, clinicians should be aware of this possibility.

  16. The effect of elevated methane pressure on methane hydrate dissociation

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.

    2004-01-01

    Methane hydrate, equilibrated at P, T conditions within the hydrate stability field, was rapidly depressurized to 1.0 or 2.0 MPa and maintained at isobaric conditions outside its stability field, while the extent and rate of hydrate dissociation was measured at fixed, externally maintained temperatures between 250 and 288 K. The dissociation rate decreases with increasing pressure at a given temperature. Dissociation rates at 1.0 MPa parallel the complex, reproducible T-dependence previously observed between 250 and 272 K at 0.1 MPa. The lowest rates were observed near 268 K, such that >50% of the sample can persist for more than two weeks at 0.1 MPa to more than a month at 1 and 2 MPa. Varying the pressure stepwise in a single experiment increased or decreased the dissociation rate in proportion to the rates observed in the isobaric experiments, similar to the rate reversibility previously observed with stepwise changes in temperature at 0.1 MPa. At fixed P, T conditions, the rate of methane hydrate dissociation decreases monotonically with time, never achieving a steady rate. The relationship between time (t) and the extent of hydrate dissociation is empirically described by: Evolved gas (%) = A??tB where the pre-exponential term A ranges from 0 to 16% s-B and the exponent B is generally <1. Based on fits of the dissociation results to Equation 1 for the full range of temperatures (204 to 289 K) and pressures (0.1 to 2.0 MPa) investigated, the derived parameters can be used to predict the methane evolution curves for pure, porous methane hydrate to within ??5%. The effects of sample porosity and the presence of quartz sand and seawater on methane hydrate dissociation are also described using Equation 1.

  17. Dissociating response systems: erasing fear from memory.

    PubMed

    Soeter, Marieke; Kindt, Merel

    2010-07-01

    In addition to the extensive evidence in animals, we previously showed that disrupting reconsolidation by noradrenergic blockade produced amnesia for the original fear response in humans. Interestingly, the declarative memory for the fear association remained intact. These results asked for a solid replication. Moreover, given the constructive nature of memories, the intact recollection of the fear association could eventually 'rebuild' the fear memory, resulting in the spontaneous recovery of the fear response. Yet, perseverance of the amnesic effects would have substantial clinical implications, as even the most effective treatments for psychiatric disorders display high percentages of relapse. Using a differential fear conditioning procedure in humans, we replicated our previous findings by showing that administering propranolol (40mg) prior to memory reactivation eliminated the startle fear response 24h later. But most importantly, this effect persisted at one month follow-up. Notably, the propranolol manipulation not only left the declarative memory for the acquired contingency untouched, but also skin conductance discrimination. In addition, a close association between declarative knowledge and skin conductance responses was found. These findings are in line with the supposed double dissociation of fear conditioning and declarative knowledge relative to the amygdala and hippocampus in humans. They support the view that skin conductance conditioning primarily reflects contingency learning, whereas the startle response is a rather specific measure of fear. Furthermore, the results indicate the absence of a causal link between the actual knowledge of a fear association and its fear response, even though they often operate in parallel. Interventions targeting the amygdalar fear memory may be essential in specifically and persistently dampening the emotional impact of fear. From a clinical and ethical perspective, disrupting reconsolidation points to promising

  18. CO chemisorption and dissociation at high coverages during CO hydrogenation on Ru catalysts.

    PubMed

    Loveless, Brett T; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-04-24

    Density functional theory (DFT) and infrared spectroscopy results are combined with mechanism-based rate equations to assess the structure and thermodynamics of chemisorbed CO (CO*) and its activation during Fischer-Tropsch synthesis (FTS). CO* binding becomes weaker with increasing coverage on Ru(0001) and Ru201 clusters, but such decreases in binding energy occur at higher coverages on Ru201 clusters than on Ru(0001) surfaces (CO*/Ru = 1.55 to 0.75); such differences appear to reflect weaker repulsive interactions on the curved surfaces prevalent on small Ru201 clusters. Ru201 clusters achieve stable supramonolayer coverages (CO*/Ru > 1) by forming geminal dicarbonyls at low-coordination corner/edge atoms. CO* infrared spectra on Ru/SiO2 (~7 nm diameter) detect mobile adlayers that anneal into denser structures at saturation. Mechanism-based FTS rate equations give activation energies that reflect the CO*-saturated surfaces prevalent during catalysis. DFT-derived barriers show that CO* predominantly reacts at (111) terraces via H-assisted reactions, consistent with measured effects of H2 and CO pressures and cluster size effects on rates and O-rejection selectivities. Barriers are much higher for unassisted CO* dissociation on (111) terraces and low-coordination atoms, including step-edge sites previously proposed as active sites for CO* dissociation during FTS. DFT-derived barriers indicate that unassisted CO* dissociation is irreversible, making such steps inconsistent with measured rates. The modest activation barriers of H-assisted CO* dissociation paths remove a requirement for special low-coordination sites for unassisted CO* activation, which is inconsistent with higher rates on larger clusters. These conclusions seem generally applicable to Co, Fe, and Ru catalysts, which show similar FTS rate equations and cluster size effects. This study also demonstrates the feasibility and relevance of DFT treatments on the curved and crowded cluster surfaces where

  19. Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study.

    PubMed

    Wang, Heng; Bozzelli, Joseph W

    2016-07-01

    Oxirane structures are important in organic synthesis, and they are important initial products in the oxidation reactions of alkyl radicals. The thermochemical properties (enthalpy of formation, entropy, and heat capacity) for the reaction steps of the unimolecular oxiranyl radical dissociation reaction are determined and compared with the available literature. The overall ring opening and subsequent steps involve four types of reactions: β-scission ring opening, intramolecular hydrogen transfer, β-scission hydrogen elimination, and β-scission methyl radical elimination. The enthalpies of formation of the transition states are determined and evaluated using six popular Density Functional Theory (DFT) calculation methods (B3LYP, B2PLYP, M06, M06-2X, ωB97X, ωB97XD), each combined with three different basis sets. The DFT enthalpy values are compared with five composite calculation methods (G3, G4, CBS-QB3, CBS-APNO, W1U), and by CCSD(T)/aug-cc-pVTZ. Kinetic parameters are determined versus pressure and temperature for the unimolecular dissociation pathways of an oxiranyl radical, which include the chemical activation reactions of the ring-opened oxiranyl radical relative to the ring-opening barrier. Multifrequency quantum Rice Ramsperger Kassel (QRRK) analysis is used to determine k(E) with master equation analysis for falloff. The major overall reaction pathway at lower combustion temperatures is oxiranyl radical dissociation to a methyl radical and carbon monoxide. Oxiranyl radical dissociation to a ketene and hydrogen atom is the key reaction path above 700 K. PMID:26990491

  20. Thermochemistry and Kinetic Analysis of the Unimolecular Oxiranyl Radical Dissociation Reaction: A Theoretical Study.

    PubMed

    Wang, Heng; Bozzelli, Joseph W

    2016-07-01

    Oxirane structures are important in organic synthesis, and they are important initial products in the oxidation reactions of alkyl radicals. The thermochemical properties (enthalpy of formation, entropy, and heat capacity) for the reaction steps of the unimolecular oxiranyl radical dissociation reaction are determined and compared with the available literature. The overall ring opening and subsequent steps involve four types of reactions: β-scission ring opening, intramolecular hydrogen transfer, β-scission hydrogen elimination, and β-scission methyl radical elimination. The enthalpies of formation of the transition states are determined and evaluated using six popular Density Functional Theory (DFT) calculation methods (B3LYP, B2PLYP, M06, M06-2X, ωB97X, ωB97XD), each combined with three different basis sets. The DFT enthalpy values are compared with five composite calculation methods (G3, G4, CBS-QB3, CBS-APNO, W1U), and by CCSD(T)/aug-cc-pVTZ. Kinetic parameters are determined versus pressure and temperature for the unimolecular dissociation pathways of an oxiranyl radical, which include the chemical activation reactions of the ring-opened oxiranyl radical relative to the ring-opening barrier. Multifrequency quantum Rice Ramsperger Kassel (QRRK) analysis is used to determine k(E) with master equation analysis for falloff. The major overall reaction pathway at lower combustion temperatures is oxiranyl radical dissociation to a methyl radical and carbon monoxide. Oxiranyl radical dissociation to a ketene and hydrogen atom is the key reaction path above 700 K.

  1. Risk Recognition, Attachment Anxiety, Self-Efficacy, and State Dissociation Predict Revictimization

    PubMed Central

    Bockers, Estelle; Roepke, Stefan; Michael, Lars; Renneberg, Babette; Knaevelsrud, Christine

    2014-01-01

    Background Previous research has identified a number of variables that constitute potential risk factors for victimization and revictimization. However, it remains unclear which factors are associated not only with childhood or adolescent victimization, but specifically with revictimization. The aim of this study was to determine whether risk recognition ability and other variables previously associated with revictimization are specifically able to differentiate individuals with childhood victimization only from revictimized individuals, and thus to predict revictimization. Methods Participants were N = 85 women aged 21 to 64 years who were interpersonally victimized in childhood or adolescence only, interpersonally revictimized in another period of life, or not victimized. A logistic regression analysis was conducted to examine whether risk recognition ability, sensation seeking, self-efficacy, state dissociation, shame, guilt, assertiveness, and attachment anxiety predicted group membership. Results The logistic regression analysis revealed risk recognition ability, attachment anxiety, state dissociation, and self-efficacy as significant predictors of revictimization. The final model accurately classified 82.4% of revictimized, 59.1% of victimized and 93.1% of non-victimized women. The overall classification rate was 80%. Conclusions This study suggests that risk recognition ability, attachment anxiety, self-efficacy, and state dissociation play a key role in revictimization. Increased risk recognition ability after an interpersonal trauma may act as a protective factor against repeated victimization that revictimized individuals may lack. A lack of increased risk recognition ability in combination with higher attachment anxiety, lower self-efficacy, and higher state dissociation may increase the risk of revictimization. PMID:25238153

  2. Hole localization, water dissociation mechanisms, and band alignment at aqueous-titania interfaces

    NASA Astrophysics Data System (ADS)

    Lyons, John L.

    Photocatalytic water splitting is a promising method for generating clean energy, but materials that can efficiently act as photocatalysts are scarce. This is in part due to the fact that exposure to water can strongly alter semiconductor surfaces and therefore photocatalyst performance. Many materials are not stable in aqueous environments; in other cases, local changes in structure may occur, affecting energy-level alignment. Even in the simplest case, dynamic fluctuations modify the organization of interface water. Accounting for such effects requires knowledge of the dominant local structural motifs and also accurate semiconductor band-edge positions, making quantitative prediction of energy-level alignments computationally challenging. Here we employ a combined theoretical approach to study the structure, energy alignment, and hole localization at aqueous-titania interfaces. We calculate the explicit aqueous-semiconductor interface using ab initio molecular dynamics, which provides the fluctuating atomic structure, the extent of water dissociation, and the resulting electrostatic potential. For both anatase and rutile TiO2 we observe spontaneous water dissociation and re-association events that occur via distinct mechanisms. We also find a higher-density water layer occurring on anatase. In both cases, we find that the second monolayer of water plays a crucial role in controlling the extent of water dissociation. Using hybrid functional calculations, we then investigate the propensity for dissociated waters to stabilize photo-excited carriers, and compare the results of rutile and anatase aqueous interfaces. Finally, we use the GW approach from many-body perturbation theory to obtain the position of semiconductor band edges relative to the occupied 1b1 level and thus the redox levels of water, and examine how local structural modifications affect these offsets. This work was performed in collaboration with N. Kharche, M. Z. Ertem, J. T. Muckerman, and M. S

  3. Light-induced dissociation of antenna complexes in the symbionts of scleractinian corals correlates with sensitivity to coral bleaching

    NASA Astrophysics Data System (ADS)

    Hill, R.; Larkum, A. W. D.; Prášil, O.; Kramer, D. M.; Szabó, M.; Kumar, V.; Ralph, P. J.

    2012-12-01

    Elevated temperatures in combination with moderate to high irradiance are known to cause bleaching events in scleractinian corals, characterised by damage to photosystem II (PSII). Photoprotective mechanisms of the symbiont can reduce the excitation pressure impinging upon PSII. In the bleaching sensitive species, Acropora millepora and Pocillopora damicornis, high light alone induced photoprotection through the xanthophyll cycle, increased content of the antioxidant carotenoid, β-carotene, as well as the dissociation of the light-harvesting chlorophyll complexes. The evidence is compatible with either the membrane-bound chlorophyll a-chlorophyll c 2-peridinin-protein (acpPC) complex or the peripheral peridinin-chlorophyll-protein complex, or both, disconnecting from PSII under high light. The acpPC complex potentially showed a state transition response with redistribution towards photosystem I to reduce PSII over-excitation. This apparent acpPC dissociation/reassociation was promoted by the addition of the xanthophyll cycle inhibitor, dithiothreitol, under high irradiance. Exposure to thermal stress as well as high light promoted xanthophyll de-epoxidation and increased β-carotene content, although it did not influence light-harvesting chlorophyll complex (LHC) dissociation, indicating light, rather than temperature, controls LHC dissociation. Photoinhibition was avoided in the bleaching tolerant species, Pavona decussata, suggesting xanthophyll cycling along with LHC dissociation may have been sufficient to prevent photodamage to PSII. Symbionts of P. decussata also displayed the greatest detachment of antenna complexes, while the more thermally sensitive species, Pocillopora damicornis and A. millepora, showed less LHC dissociation, suggesting antenna movement influences bleaching susceptibility.

  4. Thermodynamics of ion binding to phosphatidic acid bilayers. Titration calorimetry of the heat of dissociation of DMPA.

    PubMed

    Blume, A; Tuchtenhagen, J

    1992-05-19

    The heat of dissociation of the second proton of 1,2-dimyristoylphosphatidic acid (DMPA) was studied as a function of temperature using titration calorimetry. The dissociation of the second proton of DMPA was induced by addition of NaOH. From the calorimetric titration experiment, the intrinsic pK0 for the dissociation reaction could be determined by applying the Gouy-Chapman theory. pK0 decreases with temperature from ca. 6.2 at 11 degrees C to 5.4 at 54 degrees C. From the total heat of reaction, the dissociation enthalpy, delta Hdiss, was determined by subtracting the heat of neutralization of water and the heat of dilution of NaOH. In the temperature range between 2 and 23 degrees C, delta Hdiss is endothermic with an average value of ca. 2.5 kcal.mol-1 and shows no clear-cut temperature dependence. In the temperature range between 23 and 52 degrees C, delta Hdiss calculated after subtraction of the heat of neutralization and dilution is not the true dissociation enthalpy but includes contributions from the phase transition enthalpy, delta Htrans, as the pH jump induces a transition from the gel to the liquid-crystalline phase. The delta Cp for the reaction enthalpy observed in this temperature range is positive. Above 53 degrees C, the pH jump induces again only the dissociation of the second proton, and the bilayers stay in the liquid-crystalline phase. In this temperature range, delta Hdiss seems to decrease with temperature. The thermodynamic data from titration calorimetry and differential scanning calorimetry as a function of pH can be combined to construct a complete enthalpy-temperature diagram of DMPA in its two ionization states.

  5. Efficient method for calculations of ro-vibrational states in triatomic molecules near dissociation threshold: Application to ozone

    NASA Astrophysics Data System (ADS)

    Teplukhin, Alexander; Babikov, Dmitri

    2016-09-01

    A method for calculations of rotational-vibrational states of triatomic molecules up to dissociation threshold (and scattering resonances above it) is devised, that combines hyper-spherical coordinates, sequential diagonalization-truncation procedure, optimized grid DVR, and complex absorbing potential. Efficiency and accuracy of the method and new code are tested by computing the spectrum of ozone up to dissociation threshold, using two different potential energy surfaces. In both cases good agreement with results of previous studies is obtained for the lower energy states localized in the deep (˜10 000 cm-1) covalent well. Upper part of the bound state spectrum, within 600 cm-1 below dissociation threshold, is also computed and is analyzed in detail. It is found that long progressions of symmetric-stretching and bending states (up to 8 and 11 quanta, respectively) survive up to dissociation threshold and even above it, whereas excitations of the asymmetric-stretching overtones couple to the local vibration modes, making assignments difficult. Within 140 cm-1 below dissociation threshold, large-amplitude vibrational states of a floppy complex O⋯O2 are formed over the shallow van der Waals plateau. These are assigned using two local modes: the rocking-motion and the dissociative-motion progressions, up to 6 quanta in each, both with frequency ˜20 cm-1. Many of these plateau states are mixed with states of the covalent well. Interestingly, excitation of the rocking-motion helps keeping these states localized within the plateau region, by raising the effective barrier.

  6. Insights on finite size effects in ab initio study of CO adsorption and dissociation on Fe 110 surface

    NASA Astrophysics Data System (ADS)

    Chakrabarty, Aurab; Bouhali, Othmane; Mousseau, Normand; Becquart, Charlotte S.; El-Mellouhi, Fedwa

    2016-08-01

    Adsorption and dissociation of hydrocarbons on metallic surfaces represent crucial steps on the path to carburization, eventually leading to dusting corrosion. While adsorption of CO molecules on Fe surface is a barrier-less exothermic process, this is not the case for the dissociation of CO into C and O adatoms and the diffusion of C beneath the surface that are found to be associated with large energy barriers. In practice, these barriers can be affected by numerous factors that combine to favour the CO-Fe reaction such as the abundance of CO and other hydrocarbons as well as the presence of structural defects. From a numerical point of view, studying these factors is challenging and a step-by-step approach is necessary to assess, in particular, the influence of the finite box size on the reaction parameters for adsorption and dissociation of CO on metal surfaces. Here, we use density functional theory (DFT) total energy calculations with the climbing-image nudged elastic band method to estimate the adsorption energies and dissociation barriers for different CO coverages with surface supercells of different sizes. We further compute the effect of periodic boundary condition for DFT calculations and find that the contribution from van der Waals interaction in the computation of adsorption parameters is important as they contribute to correcting the finite-size error in small systems. The dissociation process involves carbon insertion into the Fe surface causing a lattice deformation that requires a larger surface system for unrestricted relaxation. We show that, in the larger surface systems associated with dilute CO-coverages, C-insertion is energetically more favourable, leading to a significant decrease in the dissociation barrier. This observation suggests that a large surface system with dilute coverage is necessary for all similar metal-hydrocarbon reactions in order to study their fundamental electronic mechanisms, as an isolated phenomenon, free from

  7. Ion mobility-mass spectrometry reveals the influence of subunit packing and charge on the dissociation of multiprotein complexes.

    PubMed

    Boeri Erba, Elisabetta; Ruotolo, Brandon T; Barsky, Daniel; Robinson, Carol V

    2010-12-01

    The composition, stoichiometry, and organization of protein complexes can be determined by collision-induced dissociation (CID) coupled to tandem mass spectrometry (MS/MS). The increased use of this approach in structural biology prompts a better understanding of the dissociation mechanism(s). Here we report a detailed investigation of the CID of two dodecameric, heat-stable and toroidally shaped complexes: heat shock protein 16.9 (HSP16.9) and stable protein 1 (SP-1). While HSP16.9 dissociates by sequential loss of unfolded monomers, SP-1 ejects not only monomers, but also its building blocks (dimers), and multiples thereof (tetramers and hexamers). Unexpectedly, the dissociation of SP-1 is strongly charge-dependent: loss of the building blocks increases with higher charge states of this complex. By combining MS/MS with ion mobility (IM-MS/MS), we have monitored the unfolding and dissociation events for these complexes in the gas phase. For HSP16.9 unfolding occurs at lower energies than the ejection of subunits, whereas for SP-1 unfolding and dissociation take place simultaneously. We consider these results in the light of the structural organization of HSP16.9 and SP-1 and hypothesize that SP-1 is unable to unfold extensively due to its particular quaternary structure and unusually high charge density. This investigation increases our understanding of the factors governing the CID of protein complexes and moves us closer to the goal of obtaining structural information on subunit interactions and packing from gas-phase experiments. PMID:21053918

  8. [Dissociative disorders: from Janet to DSM-IV].

    PubMed

    Nakatani, Y

    2000-01-01

    I reviewed the literature on dissociation and dissociative disorders from Pierre Janet to DSM-IV, and examined the current trends in research. Janet's theory on hysteria is multifaceted, and is based on three psychological models. Based on a hierarchical model, Janet related hysteric symptoms to the activities within the lower strata of mental hierarchy (automatisms psychologiques), which were demonstrably shown in somnambulism. A second model was based on the concept of a psychological system, which was hypothetically composed of ideas, images, feelings, sensations, and movements. According to this model, dissociation of psychological functions was fundamental to the mechanism of hysteria: loss of integration was thought to engender fixed ideas (ideas fixes) and to lead to the development of a system totally isolated from the whole personality system. Janet also attempted to explain various mental disorders using an economic model. He referred to a loss of equilibration between psychological force and psychological tension. Thus, an unexpected emotional experience was conceived to cause a consumption of reserved psychological force, which was in turn followed by exhaustion associated with hysteric symptoms. Whereas most current researchers regard Janet as the first to study psychological trauma as a principal cause of dissociation, I feel it is important to note that he also emphasized the role of stigmata, i.e., permanent traits of hysteric patients, which were represented as a suggestibility and a tendency toward a narrowing of the consciousness field. Discussion about dissociation and its relation to trauma all but disappeared after Janet. However, during the Second World War and post-war period, some psychiatrists began to pay attention to two emerging phenomena: a high incidence of dissociative symptoms such as fugue and amnesia among combatants, and traumatic neurosis frequently observed among ex-inmates of concentration camps. In the 1970s, interest in

  9. Intellectual functioning of inpatients with dissociative identity disorder and dissociative disorder not otherwise specified. Cognitive and neuropsychological aspects.

    PubMed

    Rossini, E D; Schwartz, D R; Braun, B G

    1996-05-01

    The intellectual functioning of 105 inpatients with multiple personality disorder and dissociative disorder not otherwise specified was assessed using the Wechsler Adult Intelligence Scale-Revised as part of a comprehensive research protocol. There were no significant intellectual differences between the groups on any major intelligence quotient summary score or any of the age-adjusted empirical factor scores. The anecdotal but widely accepted hypotheses that dissociative patients either have above average premorbid intelligence or that their current intellectual functioning is deleteriously affected by their fluctuant psychiatric disorder were not supported in this sample. A significant subsample of the multiple personality disorder group manifested abnormal interest scatter on the Wechsler Adult Intelligence Scale-Revised verbal subtests, and this variability was attributed to subtle neuropsychological deficits on the Memory/Distractibility factor. We speculate that dissociative patients might need to be evaluated for attention deficit disorder in addition to the range of dissociative symptoms in a comprehensive evaluation.

  10. The many faces of dissociation: opportunities for innovative research in psychiatry.

    PubMed

    Şar, Vedat

    2014-12-01

    It has been claimed that the progress of psychiatry has lagged behind that of other medical disciplines over the last few decades. This may suggest the need for innovative thinking and research in psychiatry, which should consider neglected areas as topics of interest in light of the potential progress which might be made in this regard. This review is concerned with one such field of psychiatry: dissociation and dissociative disorders. Dissociation is the ultimate form of human response to chronic developmental stress, because patients with dissociative disorders report the highest frequency of childhood abuse and/or neglect among all psychiatric disorders. The cardinal feature of dissociation is a disruption in one or more mental functions. Dissociative amnesia, depersonalization, derealization, identity confusion, and identity alterations are core phenomena of dissociative psychopathology which constitute a single dimension characterized by a spectrum of severity. While dissociative identity disorder (DID) is the most pervasive condition of all dissociative disorders, partial representations of this spectrum may be diagnosed as dissociative amnesia (with or without fugue), depersonalization disorder, and other specified dissociative disorders such as subthreshold DID, dissociative trance disorder, acute dissociative disorders, and identity disturbances due to exposure to oppression. In addition to constituting disorders in their own right, dissociation may accompany almost every psychiatric disorder and operate as a confounding factor in general psychiatry, including neurobiological and psycho-pharmacological research. While an anti- dissociative drug does not yet exist, appropriate psychotherapy leads to considerable improvement for many patients with dissociative disorders. PMID:25598819

  11. The many faces of dissociation: opportunities for innovative research in psychiatry.

    PubMed

    Şar, Vedat

    2014-12-01

    It has been claimed that the progress of psychiatry has lagged behind that of other medical disciplines over the last few decades. This may suggest the need for innovative thinking and research in psychiatry, which should consider neglected areas as topics of interest in light of the potential progress which might be made in this regard. This review is concerned with one such field of psychiatry: dissociation and dissociative disorders. Dissociation is the ultimate form of human response to chronic developmental stress, because patients with dissociative disorders report the highest frequency of childhood abuse and/or neglect among all psychiatric disorders. The cardinal feature of dissociation is a disruption in one or more mental functions. Dissociative amnesia, depersonalization, derealization, identity confusion, and identity alterations are core phenomena of dissociative psychopathology which constitute a single dimension characterized by a spectrum of severity. While dissociative identity disorder (DID) is the most pervasive condition of all dissociative disorders, partial representations of this spectrum may be diagnosed as dissociative amnesia (with or without fugue), depersonalization disorder, and other specified dissociative disorders such as subthreshold DID, dissociative trance disorder, acute dissociative disorders, and identity disturbances due to exposure to oppression. In addition to constituting disorders in their own right, dissociation may accompany almost every psychiatric disorder and operate as a confounding factor in general psychiatry, including neurobiological and psycho-pharmacological research. While an anti- dissociative drug does not yet exist, appropriate psychotherapy leads to considerable improvement for many patients with dissociative disorders.

  12. The Many Faces of Dissociation: Opportunities for Innovative Research in Psychiatry

    PubMed Central

    2014-01-01

    It has been claimed that the progress of psychiatry has lagged behind that of other medical disciplines over the last few decades. This may suggest the need for innovative thinking and research in psychiatry, which should consider neglected areas as topics of interest in light of the potential progress which might be made in this regard. This review is concerned with one such field of psychiatry: dissociation and dissociative disorders. Dissociation is the ultimate form of human response to chronic developmental stress, because patients with dissociative disorders report the highest frequency of childhood abuse and/or neglect among all psychiatric disorders. The cardinal feature of dissociation is a disruption in one or more mental functions. Dissociative amnesia, depersonalization, derealization, identity confusion, and identity alterations are core phenomena of dissociative psychopathology which constitute a single dimension characterized by a spectrum of severity. While dissociative identity disorder (DID) is the most pervasive condition of all dissociative disorders, partial representations of this spectrum may be diagnosed as dissociative amnesia (with or without fugue), depersonalization disorder, and other specified dissociative disorders such as subthreshold DID, dissociative trance disorder, acute dissociative disorders, and identity disturbances due to exposure to oppression. In addition to constituting disorders in their own right, dissociation may accompany almost every psychiatric disorder and operate as a confounding factor in general psychiatry, including neurobiological and psycho-pharmacological research. While an anti- dissociative drug does not yet exist, appropriate psychotherapy leads to considerable improvement for many patients with dissociative disorders. PMID:25598819

  13. Fragmentation of singly, doubly, and triply charged hydrogen deficient peptide radical cations in infrared multiphoton dissociation and electron induced dissociation.

    PubMed

    Kalli, Anastasia; Hess, Sonja

    2012-02-01

    Gas phase fragmentation of hydrogen deficient peptide radical cations continues to be an active area of research. While collision induced dissociation (CID) of singly charged species is widely examined, dissociation channels of singly and multiply charged radical cations in infrared multiphoton dissociation (IRMPD) and electron induced dissociation (EID) have not been, so far, investigated. Here, we report on the gas phase dissociation of singly, doubly and triply charged hydrogen deficient peptide radicals, [M + nH]((n+1)+·) (n=0, 1, 2), in MS(3) IRMPD and EID and compare the observed fragmentation pathways to those obtained in MS(3) CID. Backbone fragmentation in MS(3) IRMPD and EID was highly dependent on the charge state of the radical precursor ions, whereas amino acid side chain cleavages were largely independent of the charge state selected for fragmentation. Cleavages at aromatic amino acids, either through side chain loss or backbone fragmentation, were significantly enhanced over other dissociation channels. For singly charged species, the MS(3) IRMPD and EID spectra were mainly governed by radical-driven dissociation. Fragmentation of doubly and triply charged radical cations proceeded through both radical- and charge-driven processes, resulting in the formation of a wide range of backbone product ions including, a-, b-, c-, y-, x-, and z-type. While similarities existed between MS(3) CID, IRMPD, and EID of the same species, several backbone product ions and side chain losses were unique for each activation method. Furthermore, dominant dissociation pathways in each spectrum were dependent on ion activation method, amino acid composition, and charge state selected for fragmentation.

  14. COMBINES AND COMBINING.

    ERIC Educational Resources Information Center

    RIDENOUR, HARLAN E.

    THROUGH THE USE OF THIS MANUAL, VOCATIONAL AGRICULTURE STUDENTS WITH OCCUPATIONAL INTEREST IN GRAIN FARMING AND CUSTOM COMBINE OPERATION MAY GAIN KNOWLEDGE ABOUT THE BASIC DESIGN AND OPERATION OF COMBINES. DEVELOPMENT BY A STATE CURRICULUM MATERIALS DIRECTOR INCLUDED CONSULTATION WITH ENGINEERS, TRIAL, AND REVISION. OBJECTIVES ARE STATED IN TERMS…

  15. Subtypes of dissociative (conversion) disorder in two tertiary hospitals in Bangladesh.

    PubMed

    Ahsan, M S; Mullick, S I; Sobhan, M A; Khanam, M; Nahar, J S; Salam, M A; Ali, R; Islam, M; Kabir, M S

    2010-01-01

    Dissociative (conversion) disorders are common among the patients attending in and out patients of Psychiatry Department of tertiary hospitals in Bangladesh. This study was done to see the subtypes of dissociative (conversion) disorder according to International Classification of Diseases, Tenth Revision (ICD-10). This is a descriptive, cross sectional study done on 100 consecutive patients from the Departments of Psychiatry, Bangabandhu Sheikh Mujib Medical University (BSMMU), Dhaka and Dhaka Medical College Hospital (DMCH). Study period was July 2005 to June 2006. Among the patients of dissociative (conversion) disorder, mixed dissociative (conversion) disorder was found highest 34%, followed by dissociative convulsion 33%, dissociative motor disorders 19%, dissociative anaesthesia and sensory loss 5%, dissociative amnesia 4%, dissociative fugue 3%. However, the researcher did not find any multiple personality disorder which is relatively common in North America. This finding reflected that there are differences in prevalence of sub types of dissociative disorders in Bangladesh and Western countries.

  16. An outpatient clinical study of dissociative disorder not otherwise specified.

    PubMed

    Yanartaş, Ömer; Özmen, Hülya Akar; Citak, Serhat; Zincir, Selma Bozkurt; Sünbül, Esra Aydin

    2014-05-01

    The relatively high prevalence of the diagnosis of dissociative disorder not otherwise specified is frequently considered to be disproportionate. The disproportionate rate of this diagnosis is thought to be related to nosologic and/or diagnostic issues in dissociative identity disorder. We sought to investigate and compare the symptom patterns of these two clinical entities. We conducted a cross-sectional study involving 1314 participants who were screened with the Dissociative Experience Scale (DES) and the Somatoform Dissociation Questionnaire (SDQ). Of the participants, 272 who scored above the cut-off points for the screening questionnaires (DES score>30 and/or SDQ score>40 points) were invited to complete a structured interview using the Dissociative Disorders Interview Schedule (DDIS); of this subsample, only 190 participants agreed to participate in the second phase of the study. The mean score for the DES was 18.55±17.23, and the mean score for the SDQ was 30.19±13.32. Of the 190 participants, 167 patients were diagnosed as having a dissociative disorder (87.8%). We found that DD-NOS was the most prevalent category of dissociative disorder. There was a significantly larger percentage of patients in the DID group than in the DD-NOS group according to secondary features of DID and Schneiderian symptoms. The secondary features of DID and Schneiderian symptoms appeared to be more specific for DID, while no differences were detected between DID and DD-NOS based on most of the items on the SCL 90R. Further longitudinal studies are needed to determine the features that are similar and dissimilar between DD-NOS and DID. PMID:24461163

  17. An outpatient clinical study of dissociative disorder not otherwise specified.

    PubMed

    Yanartaş, Ömer; Özmen, Hülya Akar; Citak, Serhat; Zincir, Selma Bozkurt; Sünbül, Esra Aydin

    2014-05-01

    The relatively high prevalence of the diagnosis of dissociative disorder not otherwise specified is frequently considered to be disproportionate. The disproportionate rate of this diagnosis is thought to be related to nosologic and/or diagnostic issues in dissociative identity disorder. We sought to investigate and compare the symptom patterns of these two clinical entities. We conducted a cross-sectional study involving 1314 participants who were screened with the Dissociative Experience Scale (DES) and the Somatoform Dissociation Questionnaire (SDQ). Of the participants, 272 who scored above the cut-off points for the screening questionnaires (DES score>30 and/or SDQ score>40 points) were invited to complete a structured interview using the Dissociative Disorders Interview Schedule (DDIS); of this subsample, only 190 participants agreed to participate in the second phase of the study. The mean score for the DES was 18.55±17.23, and the mean score for the SDQ was 30.19±13.32. Of the 190 participants, 167 patients were diagnosed as having a dissociative disorder (87.8%). We found that DD-NOS was the most prevalent category of dissociative disorder. There was a significantly larger percentage of patients in the DID group than in the DD-NOS group according to secondary features of DID and Schneiderian symptoms. The secondary features of DID and Schneiderian symptoms appeared to be more specific for DID, while no differences were detected between DID and DD-NOS based on most of the items on the SCL 90R. Further longitudinal studies are needed to determine the features that are similar and dissimilar between DD-NOS and DID.

  18. Ion mobility spectrometry reveals duplex DNA dissociation intermediates.

    PubMed

    Burmistrova, Anastasia; Gabelica, Valérie; Duwez, Anne-Sophie; De Pauw, Edwin

    2013-11-01

    Electrospray ionization (ESI) soft desolvation is widely used to investigate fragile species such as nucleic acids. Tandem mass spectrometry (MS/MS) gives access to the gas phase energetics of the intermolecular interactions in the absence of solvent, by following the dissociation of mass-selected ions. Ion mobility mass spectrometry (IMS) provides indications on the tridimensional oligonucleotide structure by attributing a collision cross section (CCS) to the studied ion. Electrosprayed duplexes longer than eight bases pairs retain their helical structure in a solvent-free environment. However, the question of conformational changes under activation in MS/MS studies remains open. The objective of this study is to probe binding energetics and characterize the unfolding steps occurring prior to oligonucleotide duplex dissociation. Comparing the evolution of CCS with collision energy and breakdown curves, we characterize dissociation pathways involved in CID-activated DNA duplex separation into single strands, and we demonstrate here the existence of stable dissociation intermediates. At fixed duplex length, dissociation pathways were found to depend on the percentage of GC base pairs and on their position in the duplex. Our results show that pure GC sequences undergo a gradual compaction until reaching the dissociation intermediate: A-helix. Mixed AT-GC sequences were found to present at least two conformers: a classic B-helix and an extended structure where the GC tract is a B-helix and the AT tract(s) fray. The dissociation in single strands takes place from both conformers when the AT base pairs are enclosed between two GC tracts or only from the extended conformer when the AT tract is situated at the end(s) of the sequence.

  19. Calculation of the Gibbs free energy of solvation and dissociation of HCl in water via Monte Carlo simulations and continuum solvation models.

    PubMed

    McGrath, Matthew J; Kuo, I-F Will; Ngouana W, Brice F; Ghogomu, Julius N; Mundy, Christopher J; Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G; Siepmann, J Ilja

    2013-08-28

    The Gibbs free energy of solvation and dissociation of hydrogen chloride in water is calculated through a combined molecular simulation/quantum chemical approach at four temperatures between T = 300 and 450 K. The Gibbs free energy is first decomposed into the sum of two components: the Gibbs free energy of transfer of molecular HCl from the vapor to the aqueous liquid phase and the standard-state Gibbs free energy of acid dissociation of HCl in aqueous solution. The former quantity is calculated using Gibbs ensemble Monte Carlo simulations using either Kohn-Sham density functional theory or a molecular mechanics force field to determine the system's potential energy. The latter Gibbs free energy contribution is computed using a continuum solvation model utilizing either experimental reference data or micro-solvated clusters. The predicted combined solvation and dissociation Gibbs free energies agree very well with available experimental data.

  20. Valence parity to distinguish c' and z• ions from electron capture dissociation/electron transfer dissociation of peptides: effects of isomers, isobars, and proteolysis specificity.

    PubMed

    Mao, Yuan; Tipton, Jeremiah D; Blakney, Greg T; Hendrickson, Christopher L; Marshall, Alan G

    2011-10-15

    Valence parity provides a way to distinguish between N-terminal and C-terminal electron capture dissociation/electron transfer dissociation (ECD/ETD) product ions based on their number of hydrogen plus nitrogen atoms determined by accurate mass measurement and forms a basis for de novo peptide sequencing. The effect of mass accuracy (0.1-1 ppm error) on c'/z(•) overlap and unique elemental composition overlap is evaluated for a database of c'/z(•) product ions each based on all possible amino acid combinations and four subset databases containing the same c' ions but with z(•) ions determined by in silico digestion with trypsin, Glu-C, Lys-C, or chymotrypsin. High mass accuracy reduces both c'/z(•) overlap and unique elemental composition overlap. Of the four proteases, trypsin offers slightly better discrimination between N- and C-terminal ECD/ETD peptides. Interestingly, unique elemental composition overlap curves for c'/c' and z(•)/z(•) peptide ions exhibit discontinuities at certain nominal masses for 0.1-1.0 ppm mass error. Also, as noted in the companion article (Polfer et al. Anal. Chem.2011, DOI: 10.1021/ac201624t), the number of ECD/ETD product ion amino acid compositions as a function of nominal mass increases exponentially with mass but with a superimposed modulation due to higher prevalence of certain elemental compositions.

  1. Double imaging photoelectron photoion coincidence sheds new light on the dissociation of energy-selected CH3Cl(+) ions.

    PubMed

    Tang, Xiaofeng; Lin, Xiaoxiao; Zhang, Weijun; Garcia, Gustavo A; Nahon, Laurent

    2016-09-14

    The vacuum ultraviolet (VUV) photoionization and dissociative photoionization of CH3Cl in the energy range of 11-17 eV have been investigated in detail by combining synchrotron radiation and double imaging photoelectron photoion coincidences (i(2)PEPICO). Three low-lying electronic states of the CH3Cl(+) molecular ion, X(2)E, A(2)A1 and B(2)E, were prepared and analyzed. The appearance energies of the energetically accessible fragment ions, CH2Cl(+), CHCl(+), CH3(+) and CH2(+), have been obtained from their respective mass-selected threshold photoelectron spectra (TPES) or photoionization efficiency (PIE) curves. The dissociation mechanisms of energy-selected CH3Cl(+) ions, prepared in the A(2)A1 and the B(2)E electronic states, as well as outside the Franck-Condon region, have been revealed to be state-specific via ion/electron kinetic energy correlation diagrams. In particular, the umbrella mode vibrational progression of the CH3(+) fragment ion in the direct dissociation of the A(2)A1 electronic state was identified and assigned indicating that this state correlates to the CH3(+)(1(1)A1') + Cl((2)P1/2) dissociation limit, in agreement with the theoretical calculations performed in this work. PMID:27524637

  2. Dissociation of water on oxygen-covered Rh(111)

    SciTech Connect

    Shavorskiy, A.; Eralp, T.; Held, G.; Ataman, E.; Isvoranu, C.; Schnadt, J.; Andersen, J. N.

    2009-12-07

    The adsorption of water and coadsorption with oxygen on Rh(111) under ultrahigh vacuum conditions was studied using synchrotron-based photoemission and photoabsorption spectroscopy. Water adsorbs intact on the clean surface at temperatures below 154 K. Irradiation with x-rays, however, induces fast dissociation and the formation of a mixed OH+H{sub 2}O layer indicating that the partially dissociated layer is thermodynamically more stable. Coadsorption of water and oxygen at a coverage below 0.3 monolayers has a similar effect, leading to the formation of a hydrogen-bonded network of water and hydroxyl molecules at a ratio of 3:2. The partially dissociated layers are more stable than chemisorbed intact water with the maximum desorption temperatures up to 30 K higher. For higher oxygen coverage, up to 0.5 monolayers, water does not dissociate and an intact water species is observed above 160 K, which is characterized by an O 1s binding energy 0.6 eV higher than that of chemisorbed water and a high desorption temperature similar to the partially dissociated layer. The extra stabilization is most likely due to hydrogen bonds with atomic oxygen.

  3. Electron-impact dissociation and ionization of NO+ ions

    NASA Astrophysics Data System (ADS)

    Belic, D. S.; Urbain, X.; Cherkani-Hassani, H.; Defrance, P.

    2016-07-01

    Absolute cross sections for electron-impact ionization and dissociation of NO+ ions are reported. Simple ionization to NO2+ ion and production of singly charged N+ and O+ and doubly charged N2+ and O2+ fragments have been investigated. The animated electron-ion crossed-beam method is applied in the energy range from the respective thresholds up to 2.5 keV. The maximum of the simple ionization cross section is found to be (3.49 ± 0.07) × 10-17 cm2 at 135 eV. The total cross sections for N+ and O+ fragments at the maximum are found to be (13.9 ± 1.0) × 10-17 cm2 and (14.0 ± 1.4) × 10-17 cm2, respectively, both at an energy of 85 eV. By performing careful magnetic field scans of the detected signal, contributions of dissociative excitation and dissociative ionization to N+ and O+ production are determined separately. The cross sections for asymmetric dissociative ionization to N2+ and O2+ are found to be over one order of magnitude smaller. Distributions of the kinetic energy release to the fragments are determined for all dissociation processes.

  4. Enhancement of burning velocity by dissociated oxygen atoms

    NASA Astrophysics Data System (ADS)

    Akashi, Haruaki; Yoshinaga, Tomokazu; Sasaki, Koichi

    2015-09-01

    Green technology, such as preventing global warming, has been developed for years. Researches on plasma assisted combustion is one of the technologies and have been done for investigating more efficient combustion, more efficient use of fossil fuel with plasmas or applying electric fields. In the ignition time delay analyses with the dissociated oxygen atoms which is generated by non-equilibrium plasma had significant effect on the ignition time. In this paper, dissociated oxygen could effect on burning velocity or not has been examined using CHEMKIN. As a result, no effect can be seen with dissociation degree of lower than 10-3. But there is an effect on the enhancement of burning velocity with higher degree of 10-3. At the dissociation degree of 5×10-2, the burning velocity is enhanced at a factor of 1.24. And it is found that the distributions of each species in front of preheat zone are completely different. The combustion process is proceeded several steps in advance, and generation of H2O, CO and CO2 can be seen before combustion in higher dissociation case. This work was supported by KAKENHI (22340170).

  5. Electron-Impact Dissociation of Hydrocarbon Molecular Ions

    SciTech Connect

    Bannister, Mark E; Schultz, David Robert

    2014-01-01

    Absolute cross sections for electron-impact dissociation of CH_x^+ (x=1,2,3) producing CH_y^+ (y=0,1,2) fragment ions were measured in the 3-100 eV range using a crossed electron-ion beams technique with total uncertainties of about 11% near the cross section peaks. For CH^+ dissociation, although the measured energy dependence agrees well with two sets of storage ring measurements, the magnitude of the present results lies about 15% to 25% below the other results at the cross section peak near 40 eV. For dissociation of CH_2^+, the cross sections are nearly identical for energies above 15 eV, but they are dramatically different at lower energies. The CH^+ channel exhibits a strong peak rising from an observed threshold of about 6 eV; the C^+ channel is relatively flat down to the lowest measured energy. For dissociation of CH_3^+ and CD_3^+, good agreement is found with other results reported for the CH^+ fragment, but some differences are found for the CD_2^+ and C^+ fragments. A pilot study has also been undertaken to assess the feasibility of applying a molecular dynamics approach to treat the full range of electron-hydrocarbon dissociation processes, especially for energies above a few eV, in order to provide an overarching theoretical model that can be readily applied. Comparison with the experimental data for CH^+ shows favorable agreement.

  6. Autocatalytic dissociation of water at stepped transition metal surfaces

    NASA Astrophysics Data System (ADS)

    Pekoez, Rengin; Woerner, Swenja; Ghiringhelli, Luca M.; Donadio, Davide

    2014-03-01

    By means of density functional theory calculations, we investigate the adsorption and dissociation of water clusters on flat and stepped surfaces of several transition metals: Rh, Ir, Pd, Pt, and Ru. We find that water binds preferentially to the edge of the steps than to terrace sites, so that isolated clusters or one-dimensional water wires can be isolated by differential desorption. The enhanced reactivity of metal atoms at the step edge and the cooperative effect of hydrogen bonding enhance the chances of partial dissociation of water clusters on stepped surfaces. For example, water dissociation on Pt and Ir surface turns from endothermic at terraces to exothermic at steps. The interpretation of water dissociation is achieved by analyzing changes in the electronic structure of both water and metals, especially focusing on the interaction between the lone-pair electrons of water and the d-band of the metals. The shift in the energetics of water dissociation at steps is expected to play a prominent role in catalysis and fuel cells reactions, as the density of steps at surfaces could be an additional parameter to design more efficient anode materials or catalytic substrates.

  7. Dynamics of exciton dissociation in donor-acceptor polymer heterojunctions.

    PubMed

    Sun, Zhen; Stafström, Sven

    2013-04-28

    Exciton dissociation in a donor-accepter polymer heterojunction has been simulated using a nonadiabatic molecular dynamics approach, which allows for the coupled evolution of the nuclear degrees of freedom and the electronic degrees of freedom described by multiconfigurational electronic wavefunctions. The simulations reveal important details of the charge separation process: the exciton in the donor polymer first dissociates into a "hot" charge transfer state, which is best described as a polaron pair. The polaron pair can be separated into free polaron charge carriers if a sufficiently strong external electric field is applied. We have also studied the effects of inter-chain interaction, temperature, and the external electric field strength. Increasing inter-chain interactions makes it easier for the exciton to dissociate into a polaron pair state, but more difficult for the polaron pair to dissociate into free charge carriers. Higher temperature and higher electric field strength both favor exciton dissociation as well as the formation of free charge carriers. PMID:23635169

  8. Dissociative symptoms and amnesia in Dutch concentration camp survivors.

    PubMed

    Merckelbach, Harald; Dekkers, Theo; Wessel, Ineke; Roefs, Anne

    2003-01-01

    We examined to what extent dissociative phenomena in concentration camp survivors are related to post-traumatic stress symptoms. Self-reports of amnesia for traumatic war events and other dissociative experiences were studied in a sample of 31 Dutch survivors of World War II (WWII) Japanese concentration camps. Seventeen survivors treated for war-related psychiatric symptoms were compared to 14 concentration camp survivors who had no psychiatric diagnosis. Although survivors who received treatment scored significantly higher on the Impact of Event Scale and the Post-Traumatic Symptom Scale than control survivors, the two groups did not differ in terms of accessibility of war memories or dissociative experiences. Levels of post-traumatic stress symptoms were not significantly correlated with dissociative experiences. In both groups, reports of psychogenic amnesia for traumatic events were rare. Our results support previous studies demonstrating that post-traumatic stress symptoms are not necessarily accompanied by dissociative experiences. They also contradict the suggestion that amnesia is a common phenomenon in people who have been exposed to war atrocities.

  9. Deprotonated purine dissociation: experiments, computations, and astrobiological implications.

    PubMed

    Cole, Callie A; Wang, Zhe-Chen; Snow, Theodore P; Bierbaum, Veronica M

    2015-01-15

    A central focus of astrobiology is the determination of abiotic formation routes to important biomolecules. The dissociation mechanisms of these molecules lend valuable insights into their synthesis pathways. Because of the detection of organic anions in the interstellar medium (ISM), it is imperative to study their role in these syntheses. This work aims to experimentally and computationally examine deprotonated adenine and guanine dissociation in an effort to illuminate potential anionic precursors to purine formation. Collision-induced dissociation (CID) products and their branching fractions are experimentally measured using an ion trap mass spectrometer. Deprotonated guanine dissociates primarily by deammoniation (97%) with minor losses of carbodiimide (HNCNH) and/or cyanamide (NH2CN), and isocyanic acid (HNCO). Deprotonated adenine fragments by loss of hydrogen cyanide and/or isocyanide (HCN/HNC; 90%) and carbodiimide (HNCNH) and/or cyanamide (NH2CN; 10%). Tandem mass spectrometry (MS(n)) experiments reveal that deprotonated guanine fragments lose additional HCN and CO, while deprotonated adenine fragments successively lose HNC and HCN. Every neutral fragment observed in this study has been detected in the ISM, highlighting the potential for nucleobases such as these to form in such environments. Lastly, the acidity of abundant fragment ions is experimentally bracketed. Theoretical calculations at the B3LYP/6-311++G(d,p) level of theory are performed to delineate the mechanisms of dissociation and analyze the energies of reactants, intermediates, transition states, and products of these CID processes. PMID:25559322

  10. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton?

    NASA Astrophysics Data System (ADS)

    Kargel, J. S.; Prieto-Ballesteros, O.; Tanaka, K. L.

    2003-04-01

    Clathrate hydrates are potentially the most abundant class of solids in the outer Solar System. The mass of clathrates in the icy satellites may exceed that of all silicates, metals, sulfides, salts, water ice, and other non-clathrate volatiles combined. Clathrates may store most of the Solar System's (Earth's included) inventories of nonpolar condensed carbonaceous molecular gases (CO, CO_2, CH_4, and others), if the gas giants are excluded. Yet, clathrates are not inert repositories of these gases. Rather, fluctuations in temperature, pressure, and fluid composition cause the formation and destruction of clathrates. Thus, in large, geologically active worlds the nonpolar gases cycle through the solid clathrates and various fluid phases. The molar volume changes associated with clathrate formation and dissociation are substantial. The hissing and popping of terrestrial natural gas hydrate, when extracted in drill cores or dredged from the seafloor and depressurized to ambient surface conditions, is well documented and has natural analogs on larger scales. Catastrophic destabilization of clathrate due to either temperature increase or pressure decrease has been documented on Earth. For example, latest-Paleocene global warming and associated biologic extinctions are interpreted to have resulted from massive destabilization of seafloor clathrates and emission of CH_4 (G.R. Dickens et al., 1997, Geology, 25, 259-262). This event may be linked to clathrate-associated fault, slump, and landslide features widely observed on submarine ridges and edges of shelves (e.g., Dillon et al., 1998, in: J.P. Henriet and J. Mienert (Eds.), Geol. Soc. Lond. Spec. Pub. 137, 293-302) Such terrains may be good analogs of Martian chaotic terrain. Today, dynamic clathrate formation and dissociation occurs on a smaller scale, with consequent seafloor mud volcanism, mud diapirism, and seafloor sediment brecciation widely reported. Catastrophic clathrate dissociation and related events may

  11. Dissociative Identity Disorders in Korea: Two Recent Cases.

    PubMed

    Kim, Ilbin; Kim, Daeho; Jung, Hyun-Jin

    2016-03-01

    Although dissociative identity disorder (DID), the most severe of the dissociative disorders, has retained its own diagnostic entity since its introduction in the DSM-III, cases of DID are rarely seen in South and East Asia, likely due to the higher prevalence of possession disorder. We report two patients with DID who were recently admitted to our inpatient psychiatric unit and demonstrated distinct transitions to several identities. Their diagnoses were confirmed through a structured interview for dissociative disorders and possible differential diagnoses were ruled out by psychological, neuroimaging, and laboratory tests. The rapid transition to a Westernized, individualized society along with an increase in child abuse, might contribute to an increase in DID, previously under-diagnosed in this region. PMID:27081389

  12. Failure of Marine Sediments due to Gas Hydrate Dissociation

    NASA Astrophysics Data System (ADS)

    Germanovich, L.; Xu, W.

    2004-12-01

    Methane gas hydrate (MGH) dissociation in the pore space of marine sediments may be caused by various natural and human-induced processes including sea level decrease, tectonic uplift of continental margins, global warming, and petroleum operations. While these processes generally have different spatial and temporal scales, they result in MGH dissociation, and the released gas and water tend to expand. This may change the pore pressure in the sediments, affecting their mechanical state and failure processes. If the pressure does not change, the hydrate dissociation may still affect the sediment properties by perturbing particle cementation and by introducing phase interfaces (e.g., capillary menisci). In this work, the pressure change has been calculated by coupling the dissociation rate with fluid flow in the sediments based on thermodynamic considerations. The common seafloor failure, submarine landslides, can reach a length of ˜100 km, with a length-to-thickness ratio as large as ˜1000. It is often assumed that the Storegga Slides were caused by earthquakes that instantaneously created a shallow discontinuity ( ˜100 m below the seafloor) along the entire slide length of ˜100 km. Instead, Puzrin and Germanovich [2004] reasoned that the MGH dissociation may have resulted in an initial flaw at the scale of only ˜1 km. They explained the landslide evolution in submarine slopes by the mechanism of catastrophic shear band propagation of this flaw. Our modeling suggests that the sediment de-cementation and the excess pore pressure due to MGH dissociation may indeed have determined the scale of ˜1 km of this initial defect. Our calculations also suggest that dissociation-affected submarine landslides may be common for shallow sea water depths of < 1 km and involve thin sediment layers (usually ˜100 m or less). However, the MGH dissociation may also occur underneath a massive and horizontally extended MGH layer, which could serve as a seal or cap-rock. In this

  13. Case report: a convicted sex offender with dissociative identity disorder.

    PubMed

    Ross, Colin A

    2008-01-01

    A case history is presented of a man with dissociative identity disorder who was convicted of aggravated sexual assault and sentenced to 99 years in prison. According to the assailant's host personality, the rape was committed by an alter personality who wanted to punish the host by getting caught and thereby causing the host to lose his family. The rape also appeared to be an undoing of an abduction at gunpoint the man had experienced at age 11. It is important to understand the psychology of sex offenders with dissociative disorders because many will be released from prison. If even a minority of sex offenders have treatable dissociative disorders, future crimes could potentially be prevented with correct diagnosis and treatment.

  14. Dissociative Identity Disorders in Korea: Two Recent Cases.

    PubMed

    Kim, Ilbin; Kim, Daeho; Jung, Hyun-Jin

    2016-03-01

    Although dissociative identity disorder (DID), the most severe of the dissociative disorders, has retained its own diagnostic entity since its introduction in the DSM-III, cases of DID are rarely seen in South and East Asia, likely due to the higher prevalence of possession disorder. We report two patients with DID who were recently admitted to our inpatient psychiatric unit and demonstrated distinct transitions to several identities. Their diagnoses were confirmed through a structured interview for dissociative disorders and possible differential diagnoses were ruled out by psychological, neuroimaging, and laboratory tests. The rapid transition to a Westernized, individualized society along with an increase in child abuse, might contribute to an increase in DID, previously under-diagnosed in this region.

  15. Somatostatin binding to dissociated cells from rat cerebral cortex

    SciTech Connect

    Colas, B.; Prieto, J.C.; Arilla, E. )

    1990-11-01

    A method has been developed for the study of somatostatin (SS) binding to dissociated cells from rat cerebral cortex. Binding of {sup 125}I (Tyr11)SS to cells obtained by mechanical dissociation of rat cerebral cortex was dependent on time and temperature, saturable, reversible and highly specific. Under conditions of equilibrium, i.e., 60 min at 25 degrees C, native SS inhibited tracer binding in a dose-dependent manner. The Scatchard analysis of binding data was linear and yielded a dissociation constant of 0.60 +/- 0.08 nM with a maximal binding capacity of 160 +/- 16 fmol/mg protein. The binding of {sup 125}I (Tyr11)SS was specific as shown in experiments on tracer displacement by the native peptides, SS analogues, and unrelated peptides.

  16. Hopping approach towards exciton dissociation in conjugated polymers

    SciTech Connect

    Emelianova, E. V.; Auweraer, M. van der; Baessler, H.

    2008-06-14

    By employing random walk an analytic theory for the dissociation of singlet excitons in a random organic solid, for instance, a conjugated polymer, has been developed. At variance of conventional three-dimensional Onsager theory, it is assumed that an exciton with finite lifetime can first transfer endothermically an electron to an adjacent site, thereby generating a charge transfer state whose energy is above the energy of that of the initial exciton. In a second step the latter can fully dissociate in accordance with Onsager's concept Brownian motion. The results indicate that, depending of the energy required for the first jump, the first jump contributes significantly to the field dependence of the dissociation yield. Disorder weakens the temperature dependence of the yield dramatically and precludes extracting information on the exciton binding energy from it.

  17. A patient with distinct dissociative and hallucinatory fugues

    PubMed Central

    Mortati, Katherine; Grant, Arthur C

    2012-01-01

    A 62-year-old man presented with a history suggesting both dissociative fugue and a distinct fugue-like hallucination. The dissociative fugues included unplanned travel, loss of personal identity, inability to recall his past and amnesia for the fugue interval. The subjective fugues consisted of a stereotyped hallucination wherein he would travel to a social gathering place, meet his ‘imaginary friends’ and engage with them in conversation. He experienced the subjective fugues as if they were real, recognised them as hallucinations when he was normally conscious, and remembered them in great detail. A hallucinatory fugue episode occurred during video-EEG monitoring. The patient engaged in semipurposeful behaviour for which he had no memory, and the EEG demonstrated waking rhythms. Epilepsy, sleep disorder, factitious disorder and malingering were excluded from the differential diagnosis, leaving a patient with both dissociative and hallucinatory fugues, likely made possible by remote traumatic injury to limbic, arousal and motor circuits. PMID:22665872

  18. A patient with distinct dissociative and hallucinatory fugues.

    PubMed

    Mortati, Katherine; Grant, Arthur C

    2012-01-01

    A 62-year-old man presented with a history suggesting both dissociative fugue and a distinct fugue-like hallucination. The dissociative fugues included unplanned travel, loss of personal identity, inability to recall his past and amnesia for the fugue interval. The subjective fugues consisted of a stereotyped hallucination wherein he would travel to a social gathering place, meet his 'imaginary friends' and engage with them in conversation. He experienced the subjective fugues as if they were real, recognised them as hallucinations when he was normally conscious, and remembered them in great detail. A hallucinatory fugue episode occurred during video-EEG monitoring. The patient engaged in semipurposeful behaviour for which he had no memory, and the EEG demonstrated waking rhythms. Epilepsy, sleep disorder, factitious disorder and malingering were excluded from the differential diagnosis, leaving a patient with both dissociative and hallucinatory fugues, likely made possible by remote traumatic injury to limbic, arousal and motor circuits. PMID:22665872

  19. Reaction paths of phosphine dissociation on silicon (001)

    NASA Astrophysics Data System (ADS)

    Warschkow, O.; Curson, N. J.; Schofield, S. R.; Marks, N. A.; Wilson, H. F.; Radny, M. W.; Smith, P. V.; Reusch, T. C. G.; McKenzie, D. R.; Simmons, M. Y.

    2016-01-01

    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments.

  20. Photo- and collision-induced dissociation of Ar cluster ions

    NASA Astrophysics Data System (ADS)

    Kondow, Tamotsu; Nagata, Takeshi; Nonose, Shinji

    1992-04-01

    Photo- and collision- induced dissociation of an argon cluster ion, Arn+, were investigated by use of mass spectrometry. The kinetic and angular distributions of the ionic and neutral photofragments revealed two reaction pathways; dissociation of the trimeric core ion and evaporation from its solvation shell. In the Kr and Ne collisions with Arn+, the size- and collision energy- dependences of the dissociation cross sections were explained in the scheme of the charge - induced dipole, and induced dipole - induced dipole scatterings. Conversion efficiency of the collision energy into the internal energy of Arn+ was found to be proportional to the internal degrees of freedom. The upper limit of the conversion efficiency was estimated to be about 60 % in the collision energy of 0.2 eV.

  1. A patient with distinct dissociative and hallucinatory fugues.

    PubMed

    Mortati, Katherine; Grant, Arthur C

    2012-01-01

    A 62-year-old man presented with a history suggesting both dissociative fugue and a distinct fugue-like hallucination. The dissociative fugues included unplanned travel, loss of personal identity, inability to recall his past and amnesia for the fugue interval. The subjective fugues consisted of a stereotyped hallucination wherein he would travel to a social gathering place, meet his 'imaginary friends' and engage with them in conversation. He experienced the subjective fugues as if they were real, recognised them as hallucinations when he was normally conscious, and remembered them in great detail. A hallucinatory fugue episode occurred during video-EEG monitoring. The patient engaged in semipurposeful behaviour for which he had no memory, and the EEG demonstrated waking rhythms. Epilepsy, sleep disorder, factitious disorder and malingering were excluded from the differential diagnosis, leaving a patient with both dissociative and hallucinatory fugues, likely made possible by remote traumatic injury to limbic, arousal and motor circuits.

  2. Dissociative Identity Disorders in Korea: Two Recent Cases

    PubMed Central

    Kim, Ilbin; Jung, Hyun-Jin

    2016-01-01

    Although dissociative identity disorder (DID), the most severe of the dissociative disorders, has retained its own diagnostic entity since its introduction in the DSM-III, cases of DID are rarely seen in South and East Asia, likely due to the higher prevalence of possession disorder. We report two patients with DID who were recently admitted to our inpatient psychiatric unit and demonstrated distinct transitions to several identities. Their diagnoses were confirmed through a structured interview for dissociative disorders and possible differential diagnoses were ruled out by psychological, neuroimaging, and laboratory tests. The rapid transition to a Westernized, individualized society along with an increase in child abuse, might contribute to an increase in DID, previously under-diagnosed in this region. PMID:27081389

  3. The Dynamics of Dissociative Electron Attachment to Small Polyatomic Molecules

    NASA Astrophysics Data System (ADS)

    Rescigno, Thomas

    2013-09-01

    Dissociative electron attachment (DEA) is a resonant process in which an electron attaches to a molecule to form an unstable anion which subsequently fragments into stable products. DEA to small polyatomic molecules is often governed by complex electronic and nuclear dynamics that is intrinsically multi-dimensional. One-dimensional treatments of the dissociation dynamics based on resonance scattering theory, while often successful in modeling the energy dependence of total cross sections, can mask the complexity of post-attachment dynamics which is revealed by the observed angular dependence of the reaction products. The dissociation evolves on transient anion potential energy surfaces and often involves conical intersections which can result in a complete breakdown of the axial recoil approximation. I will use the examples of DEA to water, carbon dioxide and methanol to illustrate the discussion. Work performed under auspices of USDOE by LBNL under contract DE-AC02-05CH11231 and supported by OBES, Division of Chemical Sciences.

  4. O2^+ dissociation caused by an ultrashort intense laser pulse

    NASA Astrophysics Data System (ADS)

    Sayler, A. M.

    2005-05-01

    Laser-induced dissociation of O2^+ has been experimentally studied with ultrashort (˜50 fs) intense (10^14 to 10^15 W/cm^2) laser pulses at 790 nm using kinematically complete coincidence 3D momentum imaging. The resulting kinetic energy release (KER) distribution has several distinct peaks, each of which has a unique angular distribution. The lower KER features are peaked around the laser polarization, while at higher KER, dissociation perpendicular to the laser polarization is significant. For comparison, a theoretical study of O2^+ dissociation using the Electron-Nuclear Dynamics (END) approach with a laser pulse included in the time-dependent dynamics is underway. Preliminary results also indicate that ionization, which occurs predominantly at the high end of the intensity range, is strongly peaked along the laser polarization.

  5. Translation-vibration-dissociation coupling in nonequilibrium hypersonic flows

    NASA Technical Reports Server (NTRS)

    Candler, Graham

    1989-01-01

    A new simple and computationally efficient model was developed, describing the evolution of vibrational states during relaxation and dissociation. The model is based on dividing the nitrogen molecules into two types, those in the vibrational states at a lower level, whose vibrational energy is below a cutoff energy, and those in an upper level, with vibrational energy above the cutoff. Dissociation occurs at the upper level, and recombination returns molecules to the lower level. The model was applied to two flows of engineering interest, the flow through a normal Mach 15 shock wave at 60 km, and a supersonic quasi-one-dimensional flow in a nozzle. Results are compared to those obtained by existing translation-vibration-dissociation coupling models, with results indicating significant differences between the models.

  6. Reaction paths of phosphine dissociation on silicon (001).

    PubMed

    Warschkow, O; Curson, N J; Schofield, S R; Marks, N A; Wilson, H F; Radny, M W; Smith, P V; Reusch, T C G; McKenzie, D R; Simmons, M Y

    2016-01-01

    Using density functional theory and guided by extensive scanning tunneling microscopy (STM) image data, we formulate a detailed mechanism for the dissociation of phosphine (PH3) molecules on the Si(001) surface at room temperature. We distinguish between a main sequence of dissociation that involves PH2+H, PH+2H, and P+3H as observable intermediates, and a secondary sequence that gives rise to PH+H, P+2H, and isolated phosphorus adatoms. The latter sequence arises because PH2 fragments are surprisingly mobile on Si(001) and can diffuse away from the third hydrogen atom that makes up the PH3 stoichiometry. Our calculated activation energies describe the competition between diffusion and dissociation pathways and hence provide a comprehensive model for the numerous adsorbate species observed in STM experiments. PMID:26747816

  7. New-onset dissociative disorder after electroconvulsive therapy.

    PubMed

    Zaidner, Eduardo; Sewell, R Andrew; Murray, Evan; Schiller, Allen; Price, Bruce H; Cunningham, Miles G

    2010-09-01

    Electroconvulsive therapy (ECT) is an exceptionally effective treatment for a number of psychiatric conditions; however, a common adverse effect is temporary cognitive impairment, especially memory loss. The dissociative disorders also involve disturbances of memory, as well as consciousness and personal identity, but are rarely iatrogenic. We report a case in which dissociative symptoms developed after ECT. A 51-year-old woman with hypothyroidism, migraine headaches, bipolar disorder, and anorexia by history was admitted for worsening depression with suicidal ideation. After a course of 7 right-sided ECT treatments, she experienced remarkable personality change, claiming that it was 1976 and behaving as though she was 30 years younger. Neuropsychological tests were normal, and her memory and former personality spontaneously returned 2 weeks later. This case illustrates that such events may be seen in patients with certain psychiatric profiles, and further studies are needed to determine the risk factors for the occurrence of dissociative episodes after ECT.

  8. Mechanisms of peptide fragmentation from time- and energy-resolved surface-induced dissociation studies: Dissociation of angiotensin analogs

    NASA Astrophysics Data System (ADS)

    Laskin, Julia; Bailey, Thomas H.; Futrell, Jean H.

    2006-03-01

    Energetics and mechanism of dissociation of singly protonated angiotensin III (RVYIHPF) and its analogs RVYIFPF, RVYIYPF, RVYIHAF and RVYIHDF was studied using surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially configured for studying ion activation by collisions with surfaces. The energetics and dynamics of peptide fragmentation were deduced by modeling the time- and energy-resolved survival curves for each precursor ion using an RRKM-based approach developed in our laboratory. Fragmentation mechanisms were inferred from comparison of time- and energy-resolved fragmentation efficiency curves (TFECs) of different fragment ions followed by RRKM modeling of dissociation of angiotensin III into six major families of fragment ions. Detailed modeling demonstrated that dissociation of these peptides is dominated by loss of ammonia from the precursor ion and characterized by a high-energy barrier of 1.6 eV. Loss of NH3 and subsequent rearrangement of the MH+-NH3 ion results in proton mobilization and release of ca. 30 kcal/mol into internal excitation of the MH+-NH3 ion. The resulting highly excited ion accesses a variety of non-specific dissociation pathways with very high rate constants. Fast fragmentation of excited MH+-NH3 ion forms a variety of abundant bn-NH3 and an-NH3 fragment ions. Abundant XH and HX internal fragments are also formed, reflecting the stability of histidine-containing diketopiperazine structures.

  9. X-ray Computed Tomography Observation of Methane Hydrate Dissociation

    USGS Publications Warehouse

    Tomutsa, L.; Freifeld, B.; Kneafsey, T.J.; Stern, L.A.

    2002-01-01

    Deposits of naturally occurring methane hydrate have been identified in permafrost and deep oceanic environments with global reserves estimated to be twice the total amount of energy stored in fossil fuels. The fundamental behavior of methane hydrate in natural formations, while poorly understood, is of critical importance if the economic recovery of methane from hydrates is to be accomplished. In this study, computed X-ray tomography (CT) scanning is used to image an advancing dissociation front in a heterogeneous gas hydrate/sand sample at 0.1 MPa. The cylindrical methane hydrate and sand aggregate, 2.54 cm in diameter and 6.3 cm long, was contained in a PVC sample holder that was insulated on all but one end. At the uninsulated end, the dissociated gas was captured and the volume of gas monitored. The sample was initially imaged axially using X-ray CT scanning within the methane hydrate stability zone by keeping the sample temperature at 77??K. Subsequently, as the sample warmed through the methane hydrate dissociation point at 194??K and room pressure, gas was produced and the temperature at the bottom of the sample plug was monitored while CT images were acquired. The experiment showed that CT imaging can resolve the reduction in density (as seen by a reduction in beam attenuation) of the hydrate/sand aggregate due to the dissociation of methane hydrate. In addition, a comparison of CT images with gas flow and temperature measurements reveals that the CT scanner is able to resolve accurately and spatially the advancing dissociation front. Future experiments designed to better understand the thermodynamics of hydrate dissociation are planned to take advantage of the temporal and spatial resolution that the CT scanner provides.

  10. Dissociation of F-actin induced by hydrostatic pressure.

    PubMed

    Garcia, C R; Amaral Júnior, J A; Abrahamsohn, P; Verjovski-Almeida, S

    1992-11-01

    F-actin purified from rabbit skeletal muscle undergoes reversible dissociation when subjected to hydrostatic pressures up to 240 MPa. Dissociation and reversibility were detected by the following procedures: fluorescence spectral changes observed under pressure, when either intrinsic tryptophan or pyrenyl emission of N-(1-pyrenyl)iodoacetamide-labeled actin were monitored; electron microscopy of samples fixed under pressure; size-exclusion HPLC of pressurized actin. The effect of pressure upon F-actin that had been polymerized in the presence of either Mg2+, Ca2+ or K+ was studied. The standard volume changes for the association of actin subunits, calculated from pressure/dissociation curves were 74 +/- 14 ml/mol for Mg-F-actin, 79 +/- 12 ml/mol for Ca-F-actin and 328 +/- 63 ml/mol for K-F-actin, indicating that actin subunits are packed differently in the polymer depending on which cation is present. All pressure/dissociation data could be fitted by a model for dissociation of a dimer, which suggests that in the F-actin filament there is a predominant intersubunit interaction interface, most likely the head-to-tail intrastrand interaction between two subunits which repeats itself along the polymer. A tenfold change in total protein concentration from 20 micrograms to 200 micrograms/ml Mg-F-actin did not cause a change in the pressure required for half-maximal dissociation. This indicates a heterogeneity of free energy of association among actin monomers in the Mg-F-actin polymer, suggesting that, in addition to the predominant intersubunit interaction, the disordered interactions in the filament significantly contribute to the heterogeneity of microenvironments in the interface between the subunits. PMID:1425683

  11. Reversible dissociation and conformational stability of dimeric ribulose bisphosphate carboxylase.

    PubMed

    Erijman, L; Lorimer, G H; Weber, G

    1993-05-18

    Dimer-monomer dissociation of ribulosebisphosphate carboxylase/oxygenase from Rhodospirillum rubrum was investigated using hydrostatic pressure in the range 1-2 kbar to promote dissociation. Intrinsic fluorescence emission and polarization, along with the polarization of the fluorescence of single-labeled AEDANS conjugates, were used to follow the dissociation. Full reversibility after dissociation was observed to depend on the presence of small ligands: glycerol, Mg2+, and NaHCO3, the last two being required to activate the enzyme. The free energy of association at 15 degrees C, -12.9 kcal mol-1, was made up of a positive change in enthalpy on association of 6.0 kcal mol-1 and an entropic contribution (T delta S) of 18.9 kcal mol-1; thus the monomer association is entropy driven. No dissociation of the quaternary complex formed by the dimer, 2-carboxy-D-arabinitol 1,5-diphosphate (CADP), Mg2+, and NaHCO3 was observed at pressures up to 2.0 kbar; the magnitude of stabilization by the inhibitor binding was estimated as 2.3 kcal mol-1. Pressurization in the presence of bis-ANS results in a time-dependent increase in fluorophore emission, indicating changes in monomer conformation with exposure of hydrophobic surfaces upon dissociation. Reactivity against the fluorescent probe 1,5-I-AEDANS was also used as a conformational probe: HPLC of a trypsin digest of rubisco labeled at atmospheric pressure revealed a single fluorescent peptide, whereas more extensive labeling was observed when the reaction was carried out at 2.0 kbar, indicative of exposure of internal cysteines.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8388254

  12. Absolute cross sections for dissociative electron attachment to HCN and DCN

    SciTech Connect

    May, O.; Kubala, D.; Allan, M.

    2010-07-15

    Absolute partial cross sections for the formation of CN{sup -} in dissociative electron attachment to HCN and DCN have been measured using a time-of-flight ion spectrometer combined with a trochoidal electron monochromator to be 940pm{sup 2} for CN{sup -}/HCN and 340pm{sup 2} for CN{sup -}/DCN at peaks of the bands due to the {sup 2{Pi}}-shape resonance. The dissociative electron attachment bands were then recorded under higher resolution, 60 meV, with a trochoidal monochromator plus quadrupole mass filter combination and found to have a nearly vertical onset at the threshold energy and to peak at 1.85 eV. Broad structure was observed on the bands, assigned to formation of vibrationally excited CN{sup -}, from which the branching ratios could be determined to be 1,0.49, and 0.22 for the formation of CN{sup -} in the v=0,1, and 2 states, respectively. The results are compared to the recent multidimensional ab initio calculations of Chourou and Orel [Phys. Rev. A 80, 032709 (2009)].

  13. Dissociative identity disorder and schizophrenia: differential diagnosis and theoretical issues.

    PubMed

    Foote, Brad; Park, Jane

    2008-06-01

    Schizophrenia and dissociative identity disorder (DID) are typically thought of as unrelated syndromes--a genetically based psychotic disorder versus a trauma-based dissociative disorder--and are categorized as such by the DSM-IV. However, substantial data exist to document the elevated occurrence of psychotic symptoms in DID; awareness of these features is necessary to prevent diagnostic confusion. Recent research has also pointed out that schizophrenia and DID overlap not only in psychotic symptoms but also in terms of traumatic antecedents, leading to a number of suggestions for revision of our clinical, theoretical, and nosologic understanding of the relationship between these two disorders.

  14. A theoretical study on ascorbic acid dissociation in water clusters.

    PubMed

    Demianenko, Eugeniy; Ilchenko, Mykola; Grebenyuk, Anatoliy; Lobanov, Victor; Tsendra, Oksana

    2014-03-01

    Dissociation of ascorbic acid in water has been studied by using a cluster model. It was examined by density functional theory (DFT) with the В3LYP, M06, and wB97XD functionals and a 6-311++G(d,p) basis set. The thermodynamic and kinetic characteristics of proton transfer from ascorbic acid molecule to water clusters were calculated as well as the equilibrium constants (pK a ) for the related processes. The used functionals in the DFT method together with continuum solvent models provided results close to the experimental data for the dissociation constant of ascorbic acid in aqueous solution.

  15. Electron-driven excitations and dissociation of molecules

    SciTech Connect

    Miller, Greg; Orel, Ann E.

    2015-02-13

    This program studied how energy is interchanged in electron and photon collisions with molecules leading to ex-citation and dissociation. Modern ab initio techniques, both for the photoionization and electron scattering, and the subsequent nuclear dynamics studies, are used to accurately treat these problems. This work addresses vibrational ex-citation and dissociative attachment following electron impact, and the dynamics following inner shell photoionzation. These problems are ones for which a full multi-dimensional treatment of the nuclear dynamics is essential and where non-adiabatic effects are expected to be important.

  16. [Sacral fracture with spino-pelvic dissociation: a literature review].

    PubMed

    Cearra, I; Alonso, R; Martínez-Ogalla, D; Hoyos, J; Lauzirika, A; Mongil, R; Alvarez-Irusteta, E

    2013-01-01

    The term, sacral fracture with traumatic spino-pelvic dissociation, is applied to those fractures of the sacrum in which there are both transverse and sagittal fracture lines in the sacrum, leading to a mechanical dissociation of the spine and the proximal fragment of the sacrum from the remaining sacrum and the pelvis. It is a quite rare pathological condition, and probably underdiagnosed. As it usually results from a high energy multiple trauma, an early diagnosis and treatment are mandatory for a better functional prognosis. We present a literature review of this relatively unknown injury.

  17. Higher-order dynamical effects in Coulomb dissociation

    SciTech Connect

    Esbensen, H.; Bertsch, G.F.; Bertulani, C.A.

    1995-08-01

    Coulomb dissociation is a technique commonly used to extract the dipole response of nuclei far from stability. This technique is applicable if the dissociation is dominated by dipole transitions and if first-order perturbation theory is valid. In order to assess the significance of higher-order processes we solve numerically the time evolution of the wave function for a two-body breakup in the Coulomb field from a high Z target. We applied this method to the breakup reactions: {sup 11}Be {yields} {sup 10}Be + n and {sup 11}Li {yields} +2n. The latter is treated as a two-body breakup, using a di-neutron model.

  18. Dissociative tendencies and memory performance on directed-forgetting tasks.

    PubMed

    Devilly, Grant J; Ciorciari, Joseph; Piesse, Amy; Sherwell, Sarah; Zammit, Sonia; Cook, Fallon; Turton, Christie

    2007-03-01

    The current article presents two studies that aimed to replicate DePrince and Freyd's (2001, 2004) studies demonstrating that high and low dissociators differentially recall neutral and trauma words under conditions of varying cognitive load. We did not find this effect. This lack of replication was apparent for both free recall and word recognition memory and in both studies. In effect, we found little evidence to support betrayal trauma theory, yet observed increased memory fallibility, as demonstrated by lower general recall and (in one study) commission errors, in high dissociators.

  19. Local control of non-adiabatic dissociation dynamics

    NASA Astrophysics Data System (ADS)

    Bomble, L.; Chenel, A.; Meier, C.; Desouter-Lecomte, M.

    2011-05-01

    We present a theoretical approach which consists of applying the strategy of local control to projectors based on asymptotic scattering states. This allows to optimize final state distributions upon laser excitation in cases where strong non-adiabatic effects are present. The approach, despite being based on a time-local formulation, can take non-adiabatic transitions that appear at later times fully into account and adopt a corresponding control strategy. As an example, we show various dissociation channels of HeH+, a system where the ultrafast dissociation dynamics is determined by strong non-Born-Oppenheimer effects.

  20. Renner-Teller effects in HCO+ dissociative recombination

    NASA Astrophysics Data System (ADS)

    Mikhailov, Ivan A.; Kokoouline, Viatcheslav; Larson, Åsa; Tonzani, Stefano; Greene, Chris H.

    2006-09-01

    A theoretical description of the dissociative recombination process for the HCO+ ion suggests that the nonadiabatic Renner-Teller coupling between electronic and vibrational degrees of freedom plays an important role. This finding is consistent with a recent study of this process for another closed-shell molecule, the H3+ ion, where Jahn-Teller coupling was shown to generate a relatively high rate. The cross section obtained here for the dissociative recombination of HCO+ exhibits encouraging agreement with a merged-beam experiment.

  1. Caring for alcoholic patients with dissociative identity disorder.

    PubMed

    Wing, D M

    1997-01-01

    Nursing care of the alcoholic patient becomes multifaceted and complex with the presence of a psychiatric-mental health disorder. Although issues surrounding dual-diagnosis patients have been addressed in the literature, there is a paucity of research and theory regarding care of the patient who has both alcoholism and dissociative identity disorder. This article presents a synthesis of the nursing literature with the author's experience to elucidate factors that enhance healing. Nursing interventions that are unique and sensitive for the alcoholic patient with dissociative identity disorder are discussed.

  2. Distinguishing between multiple personality disorder (dissociative identity disorder) and schizophrenia using the Structured Clinical Interview for DSM-IV Dissociative Disorders.

    PubMed

    Steinberg, M; Cicchetti, D; Buchanan, J; Rakfeldt, J; Rounsaville, B

    1994-09-01

    The authors describe the systematic assessment of dissociative symptoms using the Structured Clinical Interview for DSM-IV Dissociative Disorders (SCID-D) in 50 psychiatric outpatients with a referring DSM-III-R diagnosis of either schizophrenia or schizoaffective disorder (N = 31) and subjects with multiple personality disorder (MPD [DSM-IV name change: dissociative identity disorder]; N = 19). Results indicate that patients with MPD experience significantly higher scores for five specific dissociative symptoms than patients with schizophrenia or schizoaffective disorder. The range, severity, and nature of the five dissociative symptom areas evaluated by the SCID-D distinguish MPD from the occasional occurrence of dissociative symptoms which may be seen in schizophrenia. Systematic assessment of dissociative symptoms using the SCID-D can assist in accurate differential diagnosis of MPD and schizophrenia.

  3. Dissociation of oxygen on Ag(100) induced by inelastic electron tunneling.

    PubMed

    Sprodowski, Carsten; Mehlhorn, Michael; Morgenstern, Karina

    2010-07-01

    Scanning tunneling microscopy (STM) is used to study the dissociation of molecular oxygen on Ag(100) induced by inelastic electron tunneling (IET) at 5 K. This dissociation is possible above 3.3 V with a yield of (3.63 ± 0.47) × 10(-9) per electron. Dissociation leads to three different types of hot atom motion: lateral motion, a cannon ball mechanism, and abstractive dissociation. Analysis of the I-t characteristics during dissociation suggests that the dissociation is proceeded by an adsorption site change. PMID:21386462

  4. Enhanced Dissociation of Intact Proteins with High Capacity Electron Transfer Dissociation

    NASA Astrophysics Data System (ADS)

    Riley, Nicholas M.; Mullen, Christopher; Weisbrod, Chad R.; Sharma, Seema; Senko, Michael W.; Zabrouskov, Vlad; Westphall, Michael S.; Syka, John E. P.; Coon, Joshua J.

    2016-03-01

    Electron transfer dissociation (ETD) is a valuable tool for protein sequence analysis, especially for the fragmentation of intact proteins. However, low product ion signal-to-noise often requires some degree of signal averaging to achieve high quality MS/MS spectra of intact proteins. Here we describe a new implementation of ETD on the newest generation of quadrupole-Orbitrap-linear ion trap Tribrid, the Orbitrap Fusion Lumos, for improved product ion signal-to-noise via ETD reactions on larger precursor populations. In this new high precursor capacity ETD implementation, precursor cations are accumulated in the center section of the high pressure cell in the dual pressure linear ion trap prior to charge-sign independent trapping, rather than precursor ion sequestration in only the back section as is done for standard ETD. This new scheme increases the charge capacity of the precursor accumulation event, enabling storage of approximately 3-fold more precursor charges. High capacity ETD boosts the number of matching fragments identified in a single MS/MS event, reducing the need for spectral averaging. These improvements in intra-scan dynamic range via reaction of larger precursor populations, which have been previously demonstrated through custom modified hardware, are now available on a commercial platform, offering considerable benefits for intact protein analysis and top down proteomics. In this work, we characterize the advantages of high precursor capacity ETD through studies with myoglobin and carbonic anhydrase.

  5. The development and psychometric characteristics of the Somatoform Dissociation Questionnaire (SDQ-20).

    PubMed

    Nijenhuis, E R; Spinhoven, P; Van Dyck, R; Van der Hart, O; Vanderlinden, J

    1996-11-01

    According to 19th century French psychiatry and contemporary clinical observations, dissociation pertains to both psychological and somatoform components of experience, reactions, and functions. Because such an instrument was lacking, we aimed to develop a self-reporting questionnaire measuring what we propose to call somatoform dissociation. Patients with dissociate disorder and with other DSM-IV psychiatric diagnoses completed a list of 75 items that, according to clinical experience and expert judgment, could reflect instances of somatoform dissociation. Separate logistic analyses and determination of discriminant indices per item revealed 20 items that best discriminated between those with and without dissociative disorders. Mokken analysis showed that these items are strongly scalable on a dimensional latent scale interpreted to measure somatoform dissociation. Reliability of the scale was high. Construct validity was supported by high intercorrelations with the Dissociation Questionnaire, which measures psychological dissociation, and higher scores of patients with dissociative identity disorder compared with patients with dissociative disorders not otherwise specified. In conclusion, the Somatoform Dissociation Questionnaire (SDQ-20) is a scale of good psychometric quality, which measures somatoform dissociation. The symptoms pertain to negative and positive dissociative phenomena, which were well known in 19th century French psychiatry as the mental stigmata and mental accidents of hysteria.

  6. The Reaction of Dissociative Recombination in a Strong Light Field

    SciTech Connect

    Golubkov, M. G.; Golubkov, G. V.; Adamson, S. O.; Ryabinkin, I. G.; Apukhtina, N. V.; Dementiev, A. I.

    2008-10-22

    The DR theory of slow electrons with molecular ions in strong monochromatic light field is developed. The potential energy curves of the oxygen molecule O{sub 2}** dissociative states are calculated. Classification of all possible transitions and reaction mechanisms are presented.

  7. Self-Entanglement and the Dissociation of Homonuclear Diatomic Molecules

    SciTech Connect

    Gonis, Antonios; Zhang, Xiaoguang; Nicholson, Don M; Stocks, George Malcolm

    2014-01-01

    The concept of self-entanglement is introduced to describe a mixed state or ensemble density as a pure state in an augmented Hilbert space formed by the products of the individual states forming a mixed state (or ensemble). We use this representation of mixed states to show that upon dissociation a neutral homonuclear diatomic molecule will separate into two neutral atoms.

  8. Dissociative Identity Disorder in Felonious Offenders: Two Case Studies.

    ERIC Educational Resources Information Center

    Culiner, Ty

    1997-01-01

    Describes the case studies of two inmates detained in a maximum security prison having been diagnosed with Dissociative Identity Disorder and receiving individual therapy. Although treatment is ongoing, mid-treatment progress indicates the treatment is successful and the prognosis is excellent. Accentuates the practicality and rewards of working…

  9. Clinical Assessment of Dissociative Identity Disorder among College Counseling Clients

    ERIC Educational Resources Information Center

    Levy, Benjamin; Swanson, Janine E.

    2008-01-01

    College counseling professionals address a wide range of complex student mental health concerns. Among these, accurately identifying client presentations of dissociative identity disorder (DID) can be especially challenging because students with DID sometimes present as if they are experiencing another problem, such as a mood, anxiety, or…

  10. Dissociative recombination of ammonia clusters studied by storage ring experiments

    SciTech Connect

    Oejekull, J.; Andersson, P. U.; Naagaard, M. B.; Pettersson, J. B. C.; Neau, A.; Rosen, S.; Thomas, R. D.; Larsson, M.; Semaniak, J.; Oesterdahl, F.; Danared, H.; Kaellberg, A.; Ugglas, M. af.

    2006-11-21

    Dissociative recombination of ammonia cluster ions with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The absolute cross sections for dissociative recombination of H{sup +}(NH{sub 3}){sub 2}, H{sup +}(NH{sub 3}){sub 3}, D{sup +}(ND{sub 3}){sub 2}, and D{sup +}(ND{sub 3}){sub 3} in the collision energy range of 0.001-27 eV are reported, and thermal rate coefficients for the temperature interval from 10 to 1000 K are calculated from the experimental data and compared with earlier results. The fragmentation patterns for the two ions H{sup +}(NH{sub 3}){sub 2} and D{sup +}(ND{sub 3}){sub 2} show no clear isotope effect. Dissociative recombination of X{sup +}(NX{sub 3}){sub 2} (X=H or D) is dominated by the product channels 2NX{sub 3}+X [0.95{+-}0.02 for H{sup +}(NH{sub 3}){sub 2} and 1.00{+-}0.02 for D{sup +}(ND{sub 3}){sub 2}]. Dissociative recombination of D{sup +}(ND{sub 3}){sub 3} is dominated by the channels yielding three N-containing fragments (0.95{+-}0.05)

  11. The degradation of space shuttle TPS metals in dissociated oxygen.

    NASA Technical Reports Server (NTRS)

    Gilbreath, W. P.

    1972-01-01

    The interaction of space shuttle orbiter Thermal Protection System (TPS) metals with the chemical environment to which it is exposed during reentry is considered with emphasis on the effects of dissociated oxygen. Experimental results comparing the interactions of atomic (dissociated) and molecular oxygen with five candidate shuttle TPS metals, Ni-20Cr-2ThO2, Ni-20Cr-3.5Al-2ThO2, Ni-16Cr-15Fe-2Mn-.5Si-.3La-2ThO2, Haynes Alloy Number 188, and Ti-6Al-4V at their maximum planned use temperature are presented. As measured by metal recession, weight change, rate of oxide scale formation, and scale spalling, the first four metals show enhanced degradation in a dissociated oxygen environment. The enhanced degradation appears to result from differing rates of alloy constituent reactions in the two environments. The dissociated oxygen environmental tests are found to better assess the usefulness of shuttle skin materials for the planned mission than do conventional molecular (either flowing or static) oxidation experiments.-

  12. Ion trap collision-induced dissociation of locked nucleic acids.

    PubMed

    Huang, Teng-yi; Kharlamova, Anastasia; McLuckey, Scott A

    2010-01-01

    Gas-phase dissociation of model locked nucleic acid (LNA) oligonucleotides and functional LNA-DNA chimeras have been investigated as a function of precursor ion charge state using ion trap collision-induced dissociation (CID). For the model LNA 5 and 8 mer, containing all four LNA monomers in the sequence, cleavage of all backbone bonds, generating a/w-, b/x-, c/y-, and d/z-ions, was observed with no significant preference at lower charge states. Base loss ions, except loss of thymine, from the cleavage of N-glycosidic bonds were also present. In general, complete sequence coverage was achieved in all charge states. For the two LNA-DNA chimeras, however, dramatic differences in the relative contributions of the competing dissociation channels were observed among different precursor ion charge states. At lower charge states, sequence information limited to the a-Base/w-fragment ions from cleavage of the 3'C-O bond of DNA nucleotides, except thymidine (dT), was acquired from CID of both the LNA gapmer and mixmer ions. On the other hand, extensive fragmentation from various dissociation channels was observed from post-ion/ion ion trap CID of the higher charge state ions of both LNA-DNA chimeras. This report demonstrates that tandem mass spectrometry is effective in the sequence characterization of LNA oligonucleotides and LNA-DNA chimeric therapeutics.

  13. Spectroscopic study of HNO3 dissociation on ice.

    PubMed

    Marchand, Patrick; Marcotte, Guillaume; Ayotte, Patrick

    2012-12-13

    A detailed spectroscopic study of HNO(3):H(2)O binary amorphous mixtures, and of the adsorption of HNO(3) onto ice, is reported. Using a classical optics model, the extent of intermixing and of ionic dissociation of adsorbed HNO(3), which forms a strong acid with liquid water, is determined as a function of HNO(3) coverage and temperature. Even at temperatures as low as 45 K, where intermixing is limited to at most a few molecular layers at the interface, ionic dissociation of adsorbed HNO(3) is observed to be extensive. While some amount of molecularly adsorbed HNO(3) is observed at the surface of ice at 45 K, its ionic dissociation occurs irreversibly upon heating the ice substrate to 120 K. The molecularly adsorbed state of HNO(3) is not restored upon cooling, suggesting HNO(3) is a metastable entity at the surface of ice. Therefore, despite ionic dissociation of HNO(3) being thermodynamically favored, it appears to be kinetically inhibited at the surface of amorphous solid water at temperatures below 120 K.

  14. Simulations of dissociation constants in low pressure supercritical water

    NASA Astrophysics Data System (ADS)

    Halstead, S. J.; An, P.; Zhang, S.

    2014-09-01

    This article reports molecular dynamics simulations of the dissociation of hydrochloric acid and sodium hydroxide in water from ambient to supercritical temperatures at a fixed pressure of 250 atm. Corrosion of reaction vessels is known to be a serious problem of supercritical water, and acid/base dissociation can be a significant contributing factor to this. The SPC/e model was used in conjunction with solute models determined from density functional calculations and OPLSAA Lennard-Jones parameters. Radial distribution functions were calculated, and these show a significant increase in solute-solvent ordering upon forming the product ions at all temperatures. For both dissociations, rapidly decreasing entropy of reaction was found to be the controlling thermodynamic factor, and this is thought to arise due to the ions produced from dissociation maintaining a relatively high density and ordered solvation shell compared to the reactants. The change in entropy of reaction reaches a minimum at the critical temperature. The values of pKa and pKb were calculated and both increased with temperature, in qualitative agreement with other work, until a maximum value at 748 K, after which there was a slight decrease.

  15. School Shock: Learning Disability as a Dissociative Reaction.

    ERIC Educational Resources Information Center

    Zitani, E. Alfredo

    Learning disability is suggested to be a dissociative reaction (school shock) similar to shell shock in wartime requiring appropriate theoretical and remedial approaches. Psychoanalytic and learning theory viewpoints are applied to the nature of learning disabilities. Also considered are the relation of anxiety to achievement and hypnosis to…

  16. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    ERIC Educational Resources Information Center

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  17. Photon diffractive dissociation in deep-inelastic scattering

    SciTech Connect

    Levin, E. ); Wuesthoff, M. )

    1994-10-01

    This paper is mainly devoted to the presentation and discussion of formulas for the cross section of photon diffractive dissociation. The calculations which we present in a very detailed way are based on perturbative QCD. We improve formulas which describe this process in the triple Regge limit where the square of the missing mass [ital M][sub [ital X

  18. Dissociation of the Ethyl Radical: An Exercise in Computational Chemistry

    ERIC Educational Resources Information Center

    Nassabeh, Nahal; Tran, Mark; Fleming, Patrick E.

    2014-01-01

    A set of exercises for use in a typical physical chemistry laboratory course are described, modeling the unimolecular dissociation of the ethyl radical to form ethylene and atomic hydrogen. Students analyze the computational results both qualitatively and quantitatively. Qualitative structural changes are compared to approximate predicted values…

  19. Affective Association: An Effective Intervention in Countering Fragmentation and Dissociation

    ERIC Educational Resources Information Center

    Hart, Carolyn

    2008-01-01

    This paper is concerned with the processes, both psychoanalytic and neuroscientific, involved in the undoing of dissociation in a 3-year-old, who was seen weekly over a nine month period. A neuroscientific and psychoanalytic developmental framework is used to follow a sequence of phenomena that emerged over the duration of relatively brief once…

  20. The dissociation of subjective measures of mental workload and performance

    NASA Technical Reports Server (NTRS)

    Yeh, Y. H.; Wickens, C. D.

    1984-01-01

    Dissociation between performance and subjective workload measures was investigated in the theoretical framework of the multiple resources model. Subjective measures do not preserve the vector characteristics in the multidimensional space described by the model. A theory of dissociation was proposed to locate the sources that may produce dissociation between the two workload measures. According to the theory, performance is affected by every aspect of processing whereas subjective workload is sensitive to the amount of aggregate resource investment and is dominated by the demands on the perceptual/central resources. The proposed theory was tested in three experiments. Results showed that performance improved but subjective workload was elevated with an increasing amount of resource investment. Furthermore, subjective workload was not as sensitive as was performance to differences in the amount of resource competition between two tasks. The demand on perceptual/central resources was found to be the most salient component of subjective workload. Dissociation occurred when the demand on this component was increased by the number of concurrent tasks or by the number of display elements. However, demands on response resources were weighted in subjective introspection as much as demands on perceptual/central resources. The implications of these results for workload practitioners are described.

  1. Dissociations in Processing Derivational Morphology: The Right Basal Ganglia Involvement

    ERIC Educational Resources Information Center

    Marangolo, Paola; Piras, Fabrizio

    2008-01-01

    In the neuropsychological literature, there is converging evidence for a dominant role of the left hemisphere in morphological processing. However, two right hemisphere patients were described with a clear dissociation between impaired derivational morphology and preserved inflectional processing. A recent fMRI experiment confirmed the involvement…

  2. Double Dissociations in Visual and Spatial Short-Term Memory

    ERIC Educational Resources Information Center

    Klauer, Karl Christoph; Zhao, Zengmei

    2004-01-01

    A visual short-term memory task was more strongly disrupted by visual than spatial interference, and a spatial memory task was simultaneously more strongly disrupted by spatial than visual interference. This double dissociation supports a fractionation of visuospatial short-term memory into separate visual and spatial components. In 6 experiments,…

  3. Dissociation and Mass Transfer Coefficients for Ammonia Volatilization Models

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Process-based models are being used to predict ammonia emissions from manure sources, but their accuracy has not been fully evaluated for cattle manure. Laboratory trials were conducted to measure the dissociation and mass transfer coefficients for ammonia volatilization from media of buffered ammon...

  4. Modeling Dissociation-Vibration Coupling with the Macroscopic Chemistry Method

    NASA Astrophysics Data System (ADS)

    Lilley, Charles R.; Macrossan, Michael N.

    2005-05-01

    We test the recently developed macroscopic approach to modeling chemistry in DSMC, by simulating the flow of rarefied dissociating nitrogen over a blunt cylinder. In this macroscopic method, chemical reactions are decoupled from the collision routine. Molecules are chosen to undergo dissociation at each time step, after the collisions are calculated. The required number of reaction events is calculated from macroscopic reaction rate expressions with macroscopic information taken from the time-averaged cell properties. One advantage of this method is that "state-of-the-art" macroscopic information about reaction rates can be used directly in DSMC in the same way as in continuum codes. Hybrid Navier-Stokes/DSMC codes can therefore easily use the same chemical models in both rarefied and continuum flow regions. Here we show that the macroscopic method can capture dissociation-vibration (DV) coupling, which is an important effect in vibrationally cold blunt body flows because it results in increased surface heat fluxes. We use the macroscopic method with Park's two-temperature rate model, often used in continuum studies, to capture DV coupling in DSMC. This produces a flowfield in reasonable agreement with that calculated using the conventional collision-based threshold line dissociation model.

  5. Electromagnetic dissociation effects in galactic heavy-ion fragmentation

    NASA Technical Reports Server (NTRS)

    Norbury, J. W.; Townsend, L. W.

    1986-01-01

    Methods for calculating cross sections for the breakup of galactic heavy ions by the Coulomb fields of the interacting nuclei are presented. By using the Weizsacker-Williams method of virtual quanta, estimates of electromagnetic dissociation cross sections for a variety of reactions applicable to galactic cosmic ray shielding studies are presented and compared with other predictions and with available experimental data.

  6. Perception, Action, and Roelofs Effect: A Mere Illusion of Dissociation

    PubMed Central

    2004-01-01

    A prominent and influential hypothesis of vision suggests the existence of two separate visual systems within the brain, one creating our perception of the world and another guiding our actions within it. The induced Roelofs effect has been described as providing strong evidence for this perception/action dissociation: When a small visual target is surrounded by a large frame positioned so that the frame's center is offset from the observer's midline, the perceived location of the target is shifted in the direction opposite the frame's offset. In spite of this perceptual mislocalization, however, the observer can accurately guide movements to the target location. Thus, perception is prone to the illusion while actions seem immune. Here we demonstrate that the Roelofs illusion is caused by a frame-induced transient distortion of the observer's apparent midline. We further demonstrate that actions guided to targets within this same distorted egocentric reference frame are fully expected to be accurate, since the errors of target localization will exactly cancel the errors of motor guidance. These findings provide a mechanistic explanation for the various perceptual and motor effects of the induced Roelofs illusion without requiring the existence of separate neural systems for perception and action. Given this, the behavioral dissociation that accompanies the Roelofs effect cannot be considered evidence of a dissociation of perception and action. This indicates a general need to re-evaluate the broad class of evidence purported to support this hypothesized dissociation. PMID:15510224

  7. Stochastic Approaches to Understanding Dissociations in Inflectional Morphology

    ERIC Educational Resources Information Center

    Plunkett, Kim; Bandelow, Stephan

    2006-01-01

    Computer modelling research has undermined the view that double dissociations in behaviour are sufficient to infer separability in the cognitive mechanisms underlying those behaviours. However, all these models employ "multi-modal" representational schemes, where functional specialisation of processing emerges from the training process. Targeted…

  8. Proton dependence of tobacco mosaic virus dissociation by pressure.

    PubMed

    Santos, Jose L R; Bispo, Jose A C; Landini, Gustavo F; Bonafe, Carlos F S

    2004-09-01

    Tobacco mosaic virus (TMV) is an intensely studied model of viruses. This paper reports an investigation into the dissociation of TMV by pH and pressure up to 220 MPa. The viral solution (0.25 mg/ml) incubated at 277 K showed a significant decrease in light scattering with increasing pH, suggesting dissociation. This observation was confirmed by HPLC gel filtration and electron microscopy. The calculated volume change of dissociation (DeltaV) decreased (absolute value) from -49.7 ml/mol of subunit at pH 3.8 to -21.7 ml/mol of subunit at pH 9.0. The decrease from pH 9.0 to 3.8 caused a stabilization of 14.1 kJ/mol of TMV subunit. The estimated proton release calculated from pressure-induced dissociation curves was 0.584 mol H(+)/mol of TMV subunit. These results suggest that the degree of virus inactivation by pressure and the immunogenicity of the inactivated structures can be optimized by modulating the surrounding pH. PMID:15450375

  9. Proton dependence of tobacco mosaic virus dissociation by pressure.

    PubMed

    Santos, Jose L R; Bispo, Jose A C; Landini, Gustavo F; Bonafe, Carlos F S

    2004-09-01

    Tobacco mosaic virus (TMV) is an intensely studied model of viruses. This paper reports an investigation into the dissociation of TMV by pH and pressure up to 220 MPa. The viral solution (0.25 mg/ml) incubated at 277 K showed a significant decrease in light scattering with increasing pH, suggesting dissociation. This observation was confirmed by HPLC gel filtration and electron microscopy. The calculated volume change of dissociation (DeltaV) decreased (absolute value) from -49.7 ml/mol of subunit at pH 3.8 to -21.7 ml/mol of subunit at pH 9.0. The decrease from pH 9.0 to 3.8 caused a stabilization of 14.1 kJ/mol of TMV subunit. The estimated proton release calculated from pressure-induced dissociation curves was 0.584 mol H(+)/mol of TMV subunit. These results suggest that the degree of virus inactivation by pressure and the immunogenicity of the inactivated structures can be optimized by modulating the surrounding pH.

  10. Dissociation in Children and Adolescents: A Developmental Perspective.

    ERIC Educational Resources Information Center

    Putnam, Frank W.

    From amnesia to auditory hallucinations, the symptoms of pathological dissociation are among the most devastating effects of childhood maltreatment. Ways in which therapists can provide a comprehensive developmental approach to understanding, diagnosing, and treating this challenging clinical population are presented in this text. After reviewing…

  11. Electron ionization and dissociation of aliphatic amino acids

    NASA Astrophysics Data System (ADS)

    Papp, P.; Shchukin, P.; Kočíšek, J.; Matejčík, Š.

    2012-09-01

    We present experimental and theoretical study of electron ionization and dissociative ionization to the gas phase amino acids valine, leucine, and isoleucine. A crossed electron/molecular beams technique equipped with quadrupole mass analyzer has been applied to measure mass spectra and ion efficiency curves for formation of particular ions. From experimental data the ionization energies of the molecules and the appearance energies of the fragment ions were determined. Ab initio calculations (Density Functional Theory and G3MP2 methods) were performed in order to calculate the fragmentation paths and interpret the experimental data. The experimental ionization energies of parent molecules [P]+ 8.91 ± 0.05, 8.85 ± 0.05, and 8.79 ± 0.05 eV and G3MP2 ionization energies (adiabatic) of 8.89, 8.88, and 8.81 eV were determined for valine, leucine, and isoleucine, respectively, as well as the experimental and theoretical threshold energies for dissociative ionization channels. The comparison of experimental data with calculations resulted in identification of the ions as well as the neutral fragments formed in the dissociative reactions. Around 15 mass/charge ratio fragments were identified from the mass spectra by comparison of experimental appearance energies with calculated reaction enthalpies for particular dissociative reactions.

  12. Dissociation as a Mediator of Child Abuse across Generations.

    ERIC Educational Resources Information Center

    Egeland, Byron; Susman-Stillman, Amy

    1996-01-01

    Eleven mothers who were abused and maltreated their children were compared to 10 mothers who broke the cycle of abuse. The abusing mothers were rated higher on idealization, inconsistency, and escapism in their description of their childhood, and they scored higher on the Dissociative Experience Scale than the comparison mothers. (DB)

  13. Dissociation as a mediator of child abuse across generations.

    PubMed

    Egeland, B; Susman-Stillman, A

    1996-11-01

    To test the hypothesis that dissociative process is the mechanism that accounts for the transmission of maltreatment across generations, a group of mothers who were abused and maltreated their children were compared to a group of mothers who broke the cycle of abuse. Mothers who were abused and are abusing their children were rated higher on idealization, inconsistency, and escapism in their description of their childhood and they scored higher on the Dissociative Experience Scale compared to mothers who broke the cycle. Mothers who were abused and abused their children recalled the care they received as children in a fragmented and disconnected fashion whereas those who broke the cycle integrated their abusive experience into a more coherent view of self. Even after partialing out the effects of IQ, large differences were found indicating that dissociative process plays a part in the transmission of maltreatment across generations. Possible reasons why some maltreated individuals coped with the trauma by dissociating and others integrate the experience were discussed.

  14. Child Abuse, Dissociation, and Core Beliefs in Bulimic Disorders.

    ERIC Educational Resources Information Center

    Hartt, Joanne; Waller, Glenn

    2002-01-01

    A study involving 23 British women with bulimic disorders found no dimensional relationship between any form of child abuse and bulimic pathology. However, neglect and sexual abuse were correlated with dissociation. A subset of core beliefs was associated with child abuse, with different cognitive profiles associated with each trauma. (Contains…

  15. Dynamics of Dissociative Electron Attachment to Uracil and Furane

    NASA Astrophysics Data System (ADS)

    Fonseca Dos Santos, Samantha; Douguet, Nicolas; Orel, Ann; Rescigno, Thomas

    2016-05-01

    We present the results of a theoretical study of dissociative electron attachment (DEA) to Uracil and Furan. In both cases we will present calculated angular distributions based on analysis of the entrance amplitudes obtained from the results of complex Kohn scattering calculations. For uracil, we will compare our results with available experimentally measured angular distributions obtained using the COLTRIMS method.

  16. Comment on the effectiveness of treatment for dissociative identity disorder.

    PubMed

    Ross, C A; Ellason, J

    1999-06-01

    Methodological criticisms of a recent study on treatment outcome of dissociative identity disorder are accurate: however, the outcome study is more methodologically sound than any previous work and therefore advances the field. The design of other studies and the conclusions to be drawn from the study under discussion are reviewed.

  17. Assessing the Dissociability of Recollection and Familiarity in Recognition Memory

    ERIC Educational Resources Information Center

    Pratte, Michael S.; Rouder, Jeffrey N.

    2012-01-01

    Recognition memory is often modeled as constituting 2 separate processes, recollection and familiarity, rather than as constituting a single process mediated by a generic latent strength. One way of stating evidence for the more complex 2-process model is to show dissociations with select manipulations, in which one manipulation affects…

  18. Personality features, dissociation, self-stigma, hope, and the complex treatment of depressive disorder

    PubMed Central

    Prasko, Jan; Ociskova, Marie; Grambal, Ales; Sigmundova, Zuzana; Kasalova, Petra; Marackova, Marketa; Holubova, Michaela; Vrbova, Kristyna; Latalova, Klara; Slepecky, Milos

    2016-01-01

    Objective Identifying the predictors of response to psychiatric and psychotherapeutic treatments may be useful for increasing treatment efficacy in pharmacoresistant depressive patients. The goal of this study was to examine the influence of dissociation, hope, personality trait, and selected demographic factors in treatment response of this group of patients. Methods Pharmacoresistant depressive inpatients were enrolled in the study. All patients completed Clinical Global Impression – both objective and subjective form (CGI), Beck Depression Inventory (BDI), and Beck Anxiety Inventory (BAI) at baseline and after 6 weeks of combined pharmacotherapy and psychotherapy (group cognitive-behavioral or group psychodynamic) treatment as an outcome measures. The Internalized Stigma of Mental Illness Scale (ISMI), Dissociative Experience Scale (DES), Adult Dispositional Hope Scale (ADHS), and Temperament and Character Inventory (TCI-R) were completed at the start of the treatment with the intention to find the predictors of treatment efficacy. Results The study included 72 patients who were hospitalized for the pharmacoresistant major depression; 63 of them completed the study. The mean scores of BDI-II, BAI, subjCGI, and objCGI significantly decreased during the treatment. BDI-II relative change statistically significantly correlated with the total ISMI score, Discrimination Experience (ISMI subscale), and Harm Avoidance (TCI-R personality trait). According to stepwise regression, the strongest factors connected to BDI-II relative change were the duration of the disorder and Discrimination Experience (domain of ISMI). ObjCGI relative change significantly correlated with the level of dissociation (DES), the total ISMI score, hope in ADHS total score, and Self-Directedness (TCI-R). According to stepwise regression, the strongest factor connected to objCGI relative change was Discrimination Experience (domain of ISMI). The existence of comorbid personality disorder did not

  19. Increased precision for analysis of protein-ligand dissociation constants determined from chemical shift titrations.

    PubMed

    Markin, Craig J; Spyracopoulos, Leo

    2012-06-01

    NMR is ideally suited for the analysis of protein-protein and protein ligand interactions with dissociation constants ranging from ~2 μM to ~1 mM, and with kinetics in the fast exchange regime on the NMR timescale. For the determination of dissociation constants (K ( D )) of 1:1 protein-protein or protein-ligand interactions using NMR, the protein and ligand concentrations must necessarily be similar in magnitude to the K ( D ), and nonlinear least squares analysis of chemical shift changes as a function of ligand concentration is employed to determine estimates for the parameters K ( D ) and the maximum chemical shift change (Δδ(max)). During a typical NMR titration, the initial protein concentration, [P (0)], is held nearly constant. For this condition, to determine the most accurate parameters for K ( D ) and Δδ(max) from nonlinear least squares analyses requires initial protein concentrations that are ~0.5 × K ( D ), and a maximum concentration for the ligand, or titrant, of ~10 × [P (0)]. From a practical standpoint, these requirements are often difficult to achieve. Using Monte Carlo simulations, we demonstrate that co-variation of the ligand and protein concentrations during a titration leads to an increase in the precision of the fitted K ( D ) and Δδ(max) values when [P (0)] > K ( D ). Importantly, judicious choice of protein and ligand concentrations for a given NMR titration, combined with nonlinear least squares analyses using two independent variables (ligand and protein concentrations) and two parameters (K ( D ) and Δδ(max)) is a straightforward approach to increasing the accuracy of measured dissociation constants for 1:1 protein-ligand interactions.

  20. Precision Measurement of the Ionization and Dissociation Energies of H_2, HD and D_2

    NASA Astrophysics Data System (ADS)

    Sprecher, Daniel; Liu, Jinjun; Merkt, Frédéric; Jungen, Christian; Ubachs, Wim

    2010-06-01

    The ionization and dissociation energies of H_2, HD and D_2 are benchmark quantities in molecular quantum mechanics. Comparison between experimental and theoretical values for these quantities has a long history starting with the early measurement of Beutler and the calculations of James and Coolidge. Transition wave numbers from the EF ^1Σ g^+ (v=0,N=0,1) state to selected np Rydberg states (n ≈ 60) below the X+ ^2Σ^+u (v^+=0,N^+=0,1)} ionization threshold have been measured in H_2, HD and D_2 at a precision better than 10 MHz (0.0003 cm-1). Combining the results with previous experimental and theoretical data for other energy level intervals, the ionization and dissociation energies of H_2, HD and D_2 could be determined at an absolute accuracy of better than 20 MHz. These new results represent an improvement over previous experimental results by more than one order of magnitude and the most precise values of dissociation and ionization energies measured to date in a molecular system. The results therefore offer the opportunity of a comparison with theoretical values. In particular they will be compared to the latest ab initio calculations which include nonadiabatic, relativistic and radiative effects. The comparison indicates that relativistic and radiative quantum electrodynamics corrections of order up to α^4 are needed to account for the experimental results. H. Beutler, Z. Phys. Chem. 29, 315 (1935) H. M. James and A. S. Coolidge, J. Chem. Phys. 1, 825 (1933) J. Liu, E. J. Salumbides, U. Hollenstein, J. C. J. Koelemeij, K. S. E. Eikema, W. Ubachs, and F. Merkt, J. Chem. Phys. 130, 174306 (2009) J. Liu, D. Sprecher, Ch. Jungen, W. Ubachs, and F. Merkt, submitted to J. Chem. Phys. K. Piszczatowski, G. Łach, M. Przybytek, J. Komasa, K. Pachucki, and B. Jeziorski, J. Chem. Theory Comput. 5, 3039 (2009)

  1. Dynamics of nitrogen dissociation from direct molecular simulation

    NASA Astrophysics Data System (ADS)

    Valentini, Paolo; Schwartzentruber, Thomas E.; Bender, Jason D.; Candler, Graham V.

    2016-08-01

    We present a molecular-level investigation of nitrogen dissociation at high temperature. The computational technique, called direct molecular simulation (DMS), solely relies on an ab initio potential energy surface and both N2+N2 and N +N2 processes are simulated as they concurrently take place in an evolving nonequilibrium gas system. Quasiclassical trajectory calculations (QCT) reveal that dissociation rate coefficients calculated at thermal equilibrium, i.e., assuming Boltzmann energy distributions, are approximately equal (within less than 15%) for both N2+N2 and N +N2 collisions for the range of temperatures considered. The DMS (nonequilibrium) results indicate, however, that the presence of atomic nitrogen significantly affects the dissociation rate of molecular nitrogen, but indirectly. In fact, the presence of atomic nitrogen causes an important reduction of the vibrational relaxation time of N2, by almost one order of magnitude. This, in turn, speeds up the replenishment of high-v states that are otherwise significantly depleted if only N2+N2 collisions are considered. Because of the strong favoring of dissociation from high-v states, this results in dissociation rates that are 2-3 times higher when significant atomic nitrogen is present compared to systems composed of mainly diatomic nitrogen, such as during the initial onset of dissociation. Specifically, we find that exchange events occur frequently during N +N2 collisions and that such exchange collisions constitute an effective mechanism of scrambling the internal energy states, resulting in multiquantum jumps in vibrational energy levels that effectively promote energy transfers. The resulting vibrational relaxation time constant we calculate for N +N2 collisions is significantly lower than the widely used Millikan-White model. Significant discrepancies are found between predictions of the Park two-temperature model (using the Millikan-White vibrational relaxation model) and the DMS results for

  2. Dissociation predicts later attention problems in sexually abused children

    PubMed Central

    Kaplow, Julie B.; Hall, Erin; Koenen, Karestan C.; Dodge, Kenneth A.; Amaya-Jackson, Lisa

    2008-01-01

    Objective The goals of this research are to develop and test a prospective model of attention problems in sexually abused children that includes fixed variables (e.g., gender), trauma, and disclosure-related pathways. Methods At Time 1, fixed variables, trauma variables, and stress reactions upon disclosure were assessed in 156 children aged 8 to 13 years. At the Time 2 follow-up (8 to 36 months following the initial interview), 56 of the children were assessed for attention problems. Results A path analysis involving a series of hierarchically-nested, ordinary least squares multiple regression analyses indicated two direct paths to attention problems including the child’s relationship to the perpetrator (β = .23) and dissociation measured immediately after disclosure (β = .53), while controlling for concurrent externalizing behavior (β = .43). Posttraumatic stress symptoms were only indirectly associated with attention problems via dissociation. Taken together, these pathways accounted for approximately 52% of the variance in attention problems and provided an excellent fit to the data. Conclusions Children who report dissociative symptoms upon disclosure of CSA and/or were sexually abused by someone within their family are at an increased risk of developing attention problems. Practice Implications: Findings from this study indicate that children who experienced sexual abuse at an earlier age, by someone within their family, and/or report symptoms of dissociation during disclosure are especially likely to benefit from intervention. Effective interventions should involve (1) providing emotion regulation and coping skills; and (2) helping children to process traumatic aspects of the abuse to reduce the cyclic nature of traumatic reminders leading to unmanageable stress and dissociation. PMID:18308391

  3. Radical-driven peptide backbone dissociation tandem mass spectrometry.

    PubMed

    Oh, Han Bin; Moon, Bongjin

    2015-01-01

    In recent years, a number of novel tandem mass spectrometry approaches utilizing radical-driven peptide gas-phase fragmentation chemistry have been developed. These approaches show a peptide fragmentation pattern quite different from that of collision-induced dissociation (CID). The peptide fragmentation features of these approaches share some in common with electron capture dissociation (ECD) or electron transfer dissociation (ETD) without the use of sophisticated equipment such as a Fourier-transform mass spectrometer. For example, Siu and coworkers showed that CID of transition metal (ligand)-peptide ternary complexes led to the formation of peptide radical ions through dissociative electron transfer (Chu et al., 2000. J Phys Chem B 104:3393-3397). The subsequent collisional activation of the generated radical ions resulted in a number of characteristic product ions, including a, c, x, z-type fragments and notable side-chain losses. Another example is the free radical initiated peptide sequencing (FRIPS) approach, in which Porter et al. and Beauchamp et al. independently introduced a free radical initiator to the primary amine group of the lysine side chain or N-terminus of peptides (Masterson et al., 2004. J Am Chem Soc 126:720-721; Hodyss et al., 2005 J Am Chem Soc 127: 12436-12437). Photodetachment of gaseous multiply charged peptide anions (Joly et al., 2008. J Am Chem Soc 130:13832-13833) and UV photodissociation of photolabile radical precursors including a C-I bond (Ly & Julian, 2008. J Am Chem Soc 130:351-358; Ly & Julian, 2009. J Am Soc Mass Spectrom 20:1148-1158) also provide another route to generate radical ions. In this review, we provide a brief summary of recent results obtained through the radical-driven peptide backbone dissociation tandem mass spectrometry approach.

  4. Spin-Dependent Dissociative Excitation in a Laser Pumped Afterglow.

    NASA Astrophysics Data System (ADS)

    Bohler, Christopher Lee

    The energy and spin dependence of dissociating collisions between two types of noble gas metastable atoms and cadmium dihalide molecules have been studied in a flowing afterglow apparatus. The fluorescence spectra obtained in the range of 3000-7600 A which result from the Ar( ^{3}P_2) + CdX_2 interactions indicate a dominant dissociative excitation production mechanism. On the other hand, for the He(2^3S _1) + CdX_2 collisions, there appears to be competition between dissociative excitation and other "dark" channels. The emission spectra are further used to narrow the uncertainty in the currently accepted values for the dissociation energy of the CdX _2 molecules. The Wigner spin rule (conservation of total electronic spin) was verified for these processes as shown by the dominance of final state triplet production as compared to the virtual absence of singlet spin state production. In an attempt to further study the spin dependence of the dissociative excitation process, transfer of the longitudinal component of the electronic spin from oriented He(2 ^3S_1) atoms to Cd(6 ^3S_1) atoms was monitored. These data showed a null result for the transfor of the spin component, but were limited by a 3% systematic error of the apparatus. The spin dependent measurements rely on the ability to spin-polarize the He(2^3S _1) atoms by laser optical pumping methods. Four laser materials which exhibit promising characteristics for this procedure have been studied, and the results are presented for Nd^{3+}:YAP, La_{rm 1-x}Nd _{rm x}MgAl_ {11}O_{19}, Nd^{3+}:LiNbO _3, and Nd^{3+} :Silicate fibers.

  5. Photofragment translational spectroscopy of three body dissociations and free radicals

    SciTech Connect

    North, S.W.

    1995-04-01

    This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that is invariant to the available energy. A fraction of the nascent CH{sub 3}CO radicals spontaneously dissociate following rotational averaging. The for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0{+-}1.0 kcal/mole for the barrier height, CH{sub 3}CO decomposition has been determined. The photodissociation of methyl radical at 193 nm and 212.8 nm is discussed in the chapter 5. The formation of CH{sub 2} ({sup 1}A{sub l}) and H ({sup 2}S) was the only single photon dissociation pathway observed at both wavelengths.

  6. Peas, please: a case report and neuroscientific review of dissociative amnesia and fugue.

    PubMed

    MacDonald, Kai; MacDonald, Tina

    2009-01-01

    Dissociative amnesia that encompasses one's entire life and identity is a rare disorder, as is dissociative fugue. In evaluating such cases, a dichotomy is often invoked between functional and organic etiologies. However, this dichotomy suffers from both conceptual and ethical flaws. Conceptually, putative brain-based, organic etiologies for many dissociative disorders-including dissociative amnesia-exist. Ethically, such dichotomies may result in dismissive care for patients with distress-based disorders like dissociative amnesia. In support of humane, neurobiologically informed treatment of patients with dissociative amnesia, we present excerpts from 2 post-event interviews with a patient who suffered and recovered from an episode of dissociative amnesia and fugue. Following this, we review current neurobiological models of dissociative amnesia that undermine the dichotomy of functional versus organic, and suggest that the crucial distinction in such cases is between a patient's willful, conscious deceit and processes that occur without conscious intent.

  7. Dissociation of polyoma virus by the chelation of calcium ions found associated with purified virions.

    PubMed

    Brady, J N; Winston, V D; Consigli, R A

    1977-09-01

    Analysis of polyoma virions by X-ray fluorometry demonstrated that calcium (Ca2+) was associated with the purified virion. Treatment of purified virions with ethyleneglycol-bis-N,N'-tetraacetic acid (EGTA), which chelates Ca2+, and the reducing agent dithiothreitol caused the virions to dissociate. Electron microscopy revealed that the virions were dissociated to the capsomere level. Incubation of polyoma virions with 150 mM NaCl, 10 mM EGTA, and 3 mM dithiothreitol was optimum for the dissociation reaction. The pH for the dissociation reaction ranged from 7.5 to 10.5. Cesium chloride density gradient centrifugation indicated that both EGTA and dithiothreitol were necessary for dissociation to occur; neither reagent alone dissociated the virus. The major protein product of the dissociated viral particles sedimented at 12S. Relationships between these experiments and the alkaline carbonate-bicarbonate dissociation of polyoma are discussed. PMID:197269

  8. Theoretical shaping of femtosecond laser pulses for ultrafast molecular photo-dissociation with control techniques based on time-dependent density functional theory.

    PubMed

    Castro, Alberto

    2013-05-10

    The combination of time-dependent density functional theory and quantum optimal control formalism is used to optimize the shape of ultra-short laser pulses in order to achieve the photodissociation of the hydrogen molecule. The very short pulse durations used in this work (a few femtoseconds) do not allow for significant nuclear movement during irradiation, and thus the dissociation mechanism is sequential. During pulse irradiation, a large sudden momentum is communicated which can be understood in terms of population of excited, bound or unbound, dissociative electronic states. The target is defined in terms of the average opposing force during the action of the pulse, or equivalently, in terms of the final dissociative velocity.

  9. Dissociating hippocampal subregions: double dissociation between dentate gyrus and CA1.

    PubMed

    Gilbert, P E; Kesner, R P; Lee, I

    2001-01-01

    This study presents a double dissociation between the dentate gyrus (DG) and CA1. Rats with either DG or CA1 lesions were tested on tasks requiring either spatial or spatial temporal order pattern separation. To assess spatial pattern separation, rats were trained to displace an object which covered a baited food-well. The rats were then allowed to choose between two identical objects: one covered the same well as the sample phase object (correct choice), and a second object covered a different unbaited well (incorrect choice). Spatial separations of 15-105 cm were used to separate the correct object from the incorrect object. To assess spatial temporal order pattern separation, rats were allowed to visit each arm of a radial eight-arm maze once in a randomly determined sequence. The rats were then presented with two arms and were required to choose the arm which occurred earliest in the sequence. The choice arms varied according to temporal separation (0, 2, 4, or 6) or the number of arms that occurred between the two choice arms in the sample phase sequence. On each task, once a preoperative criterion was reached, each rat was given either a DG, CA1, or control lesion and then retested. The results demonstrated that DG lesions resulted in a deficit on the spatial task but not the temporal task. In contrast, CA1 lesions resulted in a deficit on the temporal task but not the spatial task. Results suggest that the DG supports spatial pattern separation, whereas CA1 supports temporal pattern separation.

  10. Collision-induced dissociation of diazirine-labeled peptide ions. Evidence for Brønsted-acid assisted elimination of nitrogen.

    PubMed

    Marek, Aleš; Tureček, František

    2014-05-01

    Gas-phase dissociations were investigated for several peptide ions containing the Gly-Leu* N-terminal motif where Leu* was a modified norleucine residue containing the photolabile diazirine ring. Collisional activation of gas-phase peptide cations resulted in facile N₂ elimination that competed with backbone dissociations. A free lysine ammonium group can act as a Brønsted acid to facilitate N₂ elimination. This dissociation was accompanied by insertion of a lysine proton in the side chain of the photoleucine residue, as established by deuterium labeling and gas-phase sequencing of the products. Electron structure calculations were used to provide structures and energies of reactants, intermediates, and transition states for Gly-Leu*-Gly-Gly-Lys amide ions that were combined with RRKM calculations of unimolecular rate constants. The calculations indicated that Brønsted acid-catalyzed eliminations were kinetically preferred over direct loss of N₂ from the diazirine ring. Mechanisms are proposed to explain the proton-initiated reactions and discuss the reaction products. The non-catalyzed diazirine ring cleavage and N₂ loss is proposed as a thermometer dissociation for peptide ion dissociations. PMID:24549894

  11. Collision-Induced Dissociation of Diazirine-Labeled Peptide Ions. Evidence for Brønsted-Acid Assisted Elimination of Nitrogen

    NASA Astrophysics Data System (ADS)

    Marek, Aleš; Tureček, František

    2014-05-01

    Gas-phase dissociations were investigated for several peptide ions containing the Gly-Leu* N-terminal motif where Leu* was a modified norleucine residue containing the photolabile diazirine ring. Collisional activation of gas-phase peptide cations resulted in facile N2 elimination that competed with backbone dissociations. A free lysine ammonium group can act as a Brønsted acid to facilitate N2 elimination. This dissociation was accompanied by insertion of a lysine proton in the side chain of the photoleucine residue, as established by deuterium labeling and gas-phase sequencing of the products. Electron structure calculations were used to provide structures and energies of reactants, intermediates, and transition states for Gly-Leu*-Gly-Gly-Lys amide ions that were combined with RRKM calculations of unimolecular rate constants. The calculations indicated that Brønsted acid-catalyzed eliminations were kinetically preferred over direct loss of N2 from the diazirine ring. Mechanisms are proposed to explain the proton-initiated reactions and discuss the reaction products. The non-catalyzed diazirine ring cleavage and N2 loss is proposed as a thermometer dissociation for peptide ion dissociations.

  12. Dissociation dynamics of fluorinated ethene cations: from time bombs on a molecular level to double-regime dissociators.

    PubMed

    Harvey, Jonelle; Bodi, Andras; Tuckett, Richard P; Sztáray, Bálint

    2012-03-21

    The dissociative photoionization mechanism of internal energy selected C(2)H(3)F(+), 1,1-C(2)H(2)F(2)(+), C(2)HF(3)(+) and C(2)F(4)(+) cations has been studied in the 13-20 eV photon energy range using imaging photoelectron photoion coincidence spectroscopy. Five predominant channels have been found; HF loss, statistical and non-statistical F loss, cleavage of the C-C bond post H or F-atom migration, and cleavage of the C=C bond. By modelling the breakdown diagrams and ion time-of-flight distributions using statistical theory, experimental 0 K appearance energies, E(0), of the daughter ions have been determined. Both C(2)H(3)F(+) and 1,1-C(2)H(2)F(2)(+) are veritable time bombs with respect to dissociation via HF loss, where slow dissociation over a reverse barrier is followed by an explosion with large kinetic energy release. The first dissociative ionization pathway for C(2)HF(3) and C(2)F(4) involves an atom migration across the C=C bond, giving CF-CHF(2)(+) and CF-CF(3)(+), respectively, which then dissociate to form CHF(2)(+), CF(+) and CF(3)(+). The nature of the F-loss pathway has been found to be bimodal for C(2)H(3)F and 1,1-C(2)H(2)F(2), switching from statistical to non-statistical behaviour as the photon energy increases. The dissociative ionization of C(2)F(4) is found to be comprised of two regimes. At low internal energies, CF(+), CF(3)(+) and CF(2)(+) are formed in statistical processes. At high internal energies, a long-lived excited electronic state is formed, which loses an F atom in a non-statistical process and undergoes statistical redistribution of energy among the nuclear degrees of freedom. This is followed by a subsequent dissociation. In other words only the ground electronic state phase space stays inaccessible. The accurate E(0) of CF(3)(+) and CF(+) formation from C(2)F(4) together with the now well established Δ(f)H(o) of C(2)F(4) yield self-consistent enthalpies of formation for the CF(3), CF, CF(3)(+) and CF(+) species.

  13. Psychopharmacologic treatment of dissociative fugue and PTSD in an Ethiopian refugee.

    PubMed

    Liu-Barbaro, Dorothy; Stein, Murray

    2015-07-01

    Despite widespread awareness of their frequent co-occurrence, little is known about treatment of individuals with comorbid posttraumatic stress disorder (PTSD) and dissociative disorders. Patients with dissociative disorders do not respond well to standard exposure therapy, and few psychopharmacologic trials exist. Fluoxetine proved ineffective for depersonalization disorder, but paroxetine showed efficacy in decreasing dissociative symptoms in PTSD patients. PMID:26115334

  14. Neural Dissociation of Number from Letter Recognition and Its Relationship to Parietal Numerical Processing

    ERIC Educational Resources Information Center

    Park, Joonkoo; Hebrank, Andrew; Polk, Thad A.; Park, Denise C.

    2012-01-01

    The visual recognition of letters dissociates from the recognition of numbers at both the behavioral and neural level. In this article, using fMRI, we investigate whether the visual recognition of numbers dissociates from letters, thereby establishing a double dissociation. In Experiment 1, participants viewed strings of consonants and Arabic…

  15. Evaluation of the Evidence for the Trauma and Fantasy Models of Dissociation

    ERIC Educational Resources Information Center

    Dalenberg, Constance J.; Brand, Bethany L.; Gleaves, David H.; Dorahy, Martin J.; Loewenstein, Richard J.; Cardena, Etzel; Frewen, Paul A.; Carlson, Eve B.; Spiegel, David

    2012-01-01

    The relationship between a reported history of trauma and dissociative symptoms has been explained in 2 conflicting ways. Pathological dissociation has been conceptualized as a response to antecedent traumatic stress and/or severe psychological adversity. Others have proposed that dissociation makes individuals prone to fantasy, thereby…

  16. Dissociation of cephamycin C and clavulanic acid biosynthesis by 1,3-diaminopropane in Streptomyces clavuligerus.

    PubMed

    Leite, Carla A; Cavallieri, André P; Baptista, Amanda S; Araujo, Maria L G C

    2016-01-01

    Streptomyces clavuligerus produces simultaneously cephamycin C (CephC) and clavulanic acid (CA). Adding 1,3-diaminopropane to culture medium stimulates production of beta-lactam antibiotics. However, there are no studies on the influence of this diamine on coordinated production of CephC and CA. This study indicates that 1,3-diaminopropane can dissociate CephC and CA productions. Results indicated that low diamine concentrations (below 1.25 g l(-1)) in culture medium increased CA production by 200%, but not that of CephC. Conversely, CephC production increased by 300% when 10 g l(-1) 1,3-diaminopropane was added to culture medium. Addition of just L-lysine (18.3 g l(-1)) to culture medium increased both biocompounds. On the other hand, while L-lysine plus 7.5 g l(-1) 1,3-diaminopropane increased volumetric production of CephC by 1100%, its impact on CA production was insignificant. The combined results suggest that extracellular concentration of 1,3-diaminopropane may trigger the dissociation of CephC and CA biosynthesis in S. clavuligerus.

  17. Somatic and vicarious pain are represented by dissociable multivariate brain patterns

    PubMed Central

    Krishnan, Anjali; Woo, Choong-Wan; Chang, Luke J; Ruzic, Luka; Gu, Xiaosi; López-Solà, Marina; Jackson, Philip L; Pujol, Jesús; Fan, Jin; Wager, Tor D

    2016-01-01

    Understanding how humans represent others’ pain is critical for understanding pro-social behavior. ‘Shared experience’ theories propose common brain representations for somatic and vicarious pain, but other evidence suggests that specialized circuits are required to experience others’ suffering. Combining functional neuroimaging with multivariate pattern analyses, we identified dissociable patterns that predicted somatic (high versus low: 100%) and vicarious (high versus low: 100%) pain intensity in out-of-sample individuals. Critically, each pattern was at chance in predicting the other experience, demonstrating separate modifiability of both patterns. Somatotopy (upper versus lower limb: 93% accuracy for both conditions) was also distinct, located in somatosensory versus mentalizing-related circuits for somatic and vicarious pain, respectively. Two additional studies demonstrated the generalizability of the somatic pain pattern (which was originally developed on thermal pain) to mechanical and electrical pain, and also demonstrated the replicability of the somatic/vicarious dissociation. These findings suggest possible mechanisms underlying limitations in feeling others’ pain, and present new, more specific, brain targets for studying pain empathy. DOI: http://dx.doi.org/10.7554/eLife.15166.001 PMID:27296895

  18. Determination of acid dissociation constants of warfarin and hydroxywarfarins by capillary electrophoresis.

    PubMed

    Nowak, Paweł; Olechowska, Paulina; Mitoraj, Mariusz; Woźniakiewicz, Michał; Kościelniak, Paweł

    2015-08-10

    In this work the acid dissociation constants--pKa of warfarin and its all important oxidative metabolites have been determined by capillary electrophoresis-based methods. It has resulted in a complete description of two acid-base dissociation equilibria, yet not investigated experimentally for phase I metabolites of warfarin. The capillary electrophoresis (CE) method based on the relation between effective electrophoretic mobilities and pH has proven to be a suitable tool for pKa determination, while the spectrophotometric (CE-DAD) and the internal standard methods (IS-CE), have appeared to be promising alternative approaches. The CE-DAD approach based on the change in absorbance spectra between the acidic and basic forms is a combination between capillary electrophoresis and spectrophotometric titration, and yields very consistent values of pKa1 with CE. The IS-CE, in turn, enables an estimation of pKa1 and pKa2 from only two analytical runs, however, less accurate than CE and CE-DAD. The Debye-Hückel model has been confirmed experimentally as a good predictor of pKa values at various ionic strengths. Therefore, it has been used in determination of thermodynamic pKa1 and pKa2, referring to the zero ionic strength. The results are important from the analytical, pharmacological, and theoretical points of view.

  19. Resonant Infrared Multiple Photon Dissociation Spectroscopy of Anionic Nucleotide Monophosphate Clusters.

    PubMed

    Ligare, Marshall R; Rijs, Anouk M; Berden, Giel; Kabeláč, Martin; Nachtigallova, Dana; Oomens, Jos; de Vries, Mattanjah S

    2015-06-25

    We report mid-infrared spectra and potential energy surfaces of four anionic, 2'-deoxynucleotide-5'-monophosphates (dNMPs) and the ionic DNA pairs [dGMP-dCMP-H](1-), [dAMP-dTMP-H](1-) with a total charge of the complex equal to -1. We recorded IR action spectra by resonant IR multiple-photon dissociation (IRMPD) using the FELIX free electron laser. The potential energy surface study employed an on-the-fly molecular dynamics quenching method (MD/Q), using a semiempirical AM1 method, followed by an optimization of the most stable structures using density functional theory. By employing infrared multiple-photon dissociation (IRMPD) spectroscopy in combination with high-level computational methods, we aim at a better understanding of the hydrogen bonding competition between the phosphate moieties and the nucleobases. We find that, unlike in multimer double stranded DNA structures, the hydrogen bonds in these isolated nucleotide pairs are predominantly formed between the phosphate groups. This intermolecular interaction appears to exceed the stabilization energy resulting from base pairing and directs the overall cluster structure and alignment.

  20. Osmotic coefficients of aqueous weak electrolyte solutions: influence of dissociation on data reduction and modeling.

    PubMed

    Reschke, Thomas; Naeem, Shahbaz; Sadowski, Gabriele

    2012-06-28

    The experimental determination and modeling of osmotic coefficients in electrolyte solutions requires knowledge of the stoichiometric coefficient ν(i). In contrast to strong electrolytes, weak electrolytes exhibit a concentration-dependent stoichiometric coefficient, which directly influences the thermodynamic properties (e.g., osmotic coefficients). Neglecting this concentration dependence leads to erroneous osmotic coefficients for solutions of weak electrolytes. In this work, the concentration dependence of the stoichiometric coefficients and the influence of concentration on the osmotic coefficient data were accounted for by considering the dissociation equilibria of aqueous sulfuric and phosphoric acid systems. The dissociation equilibrium was combined with the ePC-SAFT equation of state to model osmotic coefficients and densities of electrolyte solutions. Without the introduction of any additional adjustable parameters, the average relative deviation between the modeled and the experimental data decreases from 12.82% to 4.28% (osmotic coefficients) and from 2.59% to 0.89% (densities) for 12 phosphoric and sulfuric systems compared to calculations that do not account for speciation. For easy access to the concentration-dependent stoichiometric coefficient, estimation schemes were formulated for mono-, di-, and triprotic acids and their salts.