Zero-Point Energy Constraint for Unimolecular Dissociation Reactions. Giving Trajectories Multiple Chances To Dissociate Correctly.

PubMed

Paul, Amit K; Hase, William L

2016-01-28

A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations.

Using Electrophoretic Mobility Shift Assays to Measure Equilibrium Dissociation Constants: GAL4-p53 Binding DNA as a Model System

ERIC Educational Resources Information Center

Heffler, Michael A.; Walters, Ryan D.; Kugel, Jennifer F.

2012-01-01

An undergraduate biochemistry laboratory experiment is described that will teach students the practical and theoretical considerations for measuring the equilibrium dissociation constant (K[subscript D]) for a protein/DNA interaction using electrophoretic mobility shift assays (EMSAs). An EMSA monitors the migration of DNA through a native gel;…

Improved Accuracy of Low Affinity Protein-Ligand Equilibrium Dissociation Constants Directly Determined by Electrospray Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Jaquillard, Lucie; Saab, Fabienne; Schoentgen, Françoise; Cadene, Martine

2012-05-01

There is continued interest in the determination by ESI-MS of equilibrium dissociation constants (KD) that accurately reflect the affinity of a protein-ligand complex in solution. Issues in the measurement of KD are compounded in the case of low affinity complexes. Here we present a KD measurement method and corresponding mathematical model dealing with both gas-phase dissociation (GPD) and aggregation. To this end, a rational mathematical correction of GPD (fsat) is combined with the development of an experimental protocol to deal with gas-phase aggregation. A guide to apply the method to noncovalent protein-ligand systems according to their kinetic behavior is provided. The approach is validated by comparing the KD values determined by this method with in-solution KD literature values. The influence of the type of molecular interactions and instrumental setup on fsat is examined as a first step towards a fine dissection of factors affecting GPD. The method can be reliably applied to a wide array of low affinity systems without the need for a reference ligand or protein.

Robust Sub-nanomolar Library Preparation for High Throughput Next Generation Sequencing.

PubMed

Wu, Wells W; Phue, Je-Nie; Lee, Chun-Ting; Lin, Changyi; Xu, Lai; Wang, Rong; Zhang, Yaqin; Shen, Rong-Fong

2018-05-04

Current library preparation protocols for Illumina HiSeq and MiSeq DNA sequencers require ≥2 nM initial library for subsequent loading of denatured cDNA onto flow cells. Such amounts are not always attainable from samples having a relatively low DNA or RNA input; or those for which a limited number of PCR amplification cycles is preferred (less PCR bias and/or more even coverage). A well-tested sub-nanomolar library preparation protocol for Illumina sequencers has however not been reported. The aim of this study is to provide a much needed working protocol for sub-nanomolar libraries to achieve outcomes as informative as those obtained with the higher library input (≥ 2 nM) recommended by Illumina's protocols. Extensive studies were conducted to validate a robust sub-nanomolar (initial library of 100 pM) protocol using PhiX DNA (as a control), genomic DNA (Bordetella bronchiseptica and microbial mock community B for 16S rRNA gene sequencing), messenger RNA, microRNA, and other small noncoding RNA samples. The utility of our protocol was further explored for PhiX library concentrations as low as 25 pM, which generated only slightly fewer than 50% of the reads achieved under the standard Illumina protocol starting with > 2 nM. A sub-nanomolar library preparation protocol (100 pM) could generate next generation sequencing (NGS) results as robust as the standard Illumina protocol. Following the sub-nanomolar protocol, libraries with initial concentrations as low as 25 pM could also be sequenced to yield satisfactory and reproducible sequencing results.

Dissociation constants, neutralization enthalpies and reactions of 3-styryl-2-mercaptopropenoic and 3-(1-naphthyl)-2-mercaptopropenoic acids.

PubMed

Izquierdo, A; Bosch, E; Beltran, J L

1984-06-01

Dissociation constants (pK(a1) and pK(a2) in water-ethanol medium for 3-styryl-2-mercaptopropenoic and 3-(1-naphthyl)-2-mercaptopropenoic acid have been determined potentiometrically, and pK(a2) for both in aqueous medium, spectrophotometrically. Neutralization enthalpies in water-ethanol medium have been determined by thermometric titration. The reactions with metal ions have been studied, and the main reactions are described. The most sensitive reactions are with titanium(IV) (pD = 7.00) and nickel(II) (pD = 6.50).

A new sensitive method of dissociation constants determination based on the isohydric solutions principle.

PubMed

Michałowski, Tadeusz; Pilarski, Bogusław; Asuero, Agustin G; Dobkowska, Agnieszka

2010-10-15

The paper provides a new formulation and analytical proposals based on the isohydric solutions concept. It is particularly stated that a mixture formed, according to titrimetric mode, from a weak acid (HX, C(0)mol/L) and a strong acid (HB, Cmol/L) solutions, assumes constant pH, independently on the volumes of the solutions mixed, provided that the relation C(0)=C+C(2)·10(pK(1)) is valid, where pK(1)=-log K(1), K(1) the dissociation constant for HX. The generalized formulation, referred to the isohydric solutions thus obtained, was extended also to more complex acid-base systems. Particularly in the (HX, HB) system, the titration occurs at constant ionic strength (I) value, not resulting from presence of a basal electrolyte. This very advantageous conjunction of the properties provides, among others, a new, very sensitive method for verification of pK(1) value. The new method is particularly useful for weak acids HX characterized by low pK(1) values. The method was tested experimentally on four acid-base systems (HX, HB), in aqueous and mixed-solvent media and compared with the literature data. Some useful (linear and hyperbolic) correlations were stated and applied for validation of pK(1) values. Finally, some practical applications of analytical interest of the isohydricity (pH constancy) principle as one formulated in this paper were enumerated, proving the usefulness of such a property which has its remote roots in the Arrhenius concept. Copyright © 2010 Elsevier B.V. All rights reserved.

Measurement of the Dissociation-Equilibrium Constants for Low Affinity Antibiotic Binding Interaction with Bacterial Ribosomes by the T2 (CPMG) and Line-Broadening Methods

NASA Astrophysics Data System (ADS)

Verdier, L.; Gharbi-Benarous, J.; Bertho, G.; Mauvais, P.; Girault, J.-P.

1999-10-01

In this study the dissociation constants of the low antibiotic-ribosomes interaction were determined by the T2 (CPMG), the Carr-Purcell-Meiboom-Gill spin-echo decay rate and the line-broadening methods. Three MLSB antibiotics were studied, a macrolide roxithromycin, a ketolide HMR 3647 and a lincosamide clindamycin for their weak interaction with three bacterial ribosomes, E. coli, Staphylococcus aureus sensitive and resistant to erythromycin. Nous avons mesuré la constante de dissociation, Kd correspondant à l'interaction faible antibiotique-ribosome bactérien pour des antibiotiques de différentes classes, un macrolide (roxithromycine), un kétolide (HMR 3647) et une lincosamide (clindamycine) avec des ribosomes de différentes souches bactériennes (E. coli, Staphylococcus aureus sensible ou résistant à l'erythromycin) par deux méthodes : l'une basée sur la variation des largeurs de raies et l'autre sur les temps de relaxation transversaux T2 en utilisant une séquence CPMG.

Simultaneous estimation of intracellular free Mg2+ and pH by use of a new pH-dependent dissociation constant of MgATP.

PubMed

Nakayama, Shinsuke; Nomura, Hideki; Smith, Lorraine M; Clark, Joseph F

2002-06-01

In the present technical note for 31P-NMR, we used a new pH-dependent dissociation constant of MgATP, and re-estimated changes in the intracellular free Mg2+ concentration and pH from the chemical shifts of beta- and gamma-ATP during Na+-removal in smooth muscle. We confirmed the role of Na+ - Mg2+ exchange.

Determination of the Acid Dissociation Constant of a Phenolic Acid by High Performance Liquid Chromatography: An Experiment for the Upper Level Analytical Chemistry Laboratory

ERIC Educational Resources Information Center

Raboh, Ghada

2018-01-01

A high performance liquid chromatography (HPLC) experiment for the upper level analytical chemistry laboratory is described. The students consider the effect of mobile-phase composition and pH on the retention times of ionizable compounds in order to determine the acid dissociation constant, K[subscript a], of a phenolic acid. Results are analyzed…

Sequence-specific, nanomolar peptide binding via cucurbit[8]uril-induced folding and inclusion of neighboring side chains.

PubMed

Smith, Lauren C; Leach, David G; Blaylock, Brittney E; Ali, Omar A; Urbach, Adam R

2015-03-18

This paper describes the molecular recognition of the tripeptide Tyr-Leu-Ala by the synthetic receptor cucurbit[8]uril (Q8) in aqueous buffer with nanomolar affinity and exceptional specificity. This combination of characteristics, which also applies to antibodies, is desirable for applications in biochemistry and biotechnology but has eluded supramolecular chemists for decades. Building on prior knowledge that Q8 binds to peptides with N-terminal aromatic residues, a library screen of 105 peptides was designed to test the effects of residues adjacent to N-terminal Trp, Phe, or Tyr. The screen used tetramethylbenzobis(imidazolium) (MBBI) as a fluorescent indicator and resulted in the unexpected discovery that MBBI can serve not only as a turn-off sensor via the simultaneous inclusion of a Trp residue but also as a turn-on sensor via the competitive displacement of MBBI upon binding of Phe- or Tyr-terminated peptides. The unusual fluorescence response of the Tyr series prompted further investigation by (1)H NMR spectroscopy, electrospray ionization mass spectrometry, and isothermal titration calorimetry. From these studies, a novel binding motif was discovered in which only 1 equiv of peptide binds to Q8, and the side chains of both the N-terminal Tyr residue and its immediate neighbor bind within the Q8 cavity. For the peptide Tyr-Leu-Ala, the equilibrium dissociation constant value is 7.2 nM, whereas that of its sequence isomer Tyr-Ala-Leu is 34 μM. The high stability, recyclability, and low cost of Q8 combined with the straightforward incorporation of Tyr-Leu-Ala into recombinant proteins should make this system attractive for the development of biological applications.

Determination of equilibrium dissociation constants for recombinant antibodies by high-throughput affinity electrophoresis.

PubMed

Pan, Yuchen; Sackmann, Eric K; Wypisniak, Karolina; Hornsby, Michael; Datwani, Sammy S; Herr, Amy E

2016-12-23

High-quality immunoreagents enhance the performance and reproducibility of immunoassays and, in turn, the quality of both biological and clinical measurements. High quality recombinant immunoreagents are generated using antibody-phage display. One metric of antibody quality - the binding affinity - is quantified through the dissociation constant (K D ) of each recombinant antibody and the target antigen. To characterize the K D of recombinant antibodies and target antigen, we introduce affinity electrophoretic mobility shift assays (EMSAs) in a high-throughput format suitable for small volume samples. A microfluidic card comprised of free-standing polyacrylamide gel (fsPAG) separation lanes supports 384 concurrent EMSAs in 30 s using a single power source. Sample is dispensed onto the microfluidic EMSA card by acoustic droplet ejection (ADE), which reduces EMSA variability compared to sample dispensing using manual or pin tools. The K D for each of a six-member fragment antigen-binding fragment library is reported using ~25-fold less sample mass and ~5-fold less time than conventional heterogeneous assays. Given the form factor and performance of this micro- and mesofluidic workflow, we have developed a sample-sparing, high-throughput, solution-phase alternative for biomolecular affinity characterization.

Determination of equilibrium dissociation constants for recombinant antibodies by high-throughput affinity electrophoresis

PubMed Central

Pan, Yuchen; Sackmann, Eric K.; Wypisniak, Karolina; Hornsby, Michael; Datwani, Sammy S.; Herr, Amy E.

2016-01-01

High-quality immunoreagents enhance the performance and reproducibility of immunoassays and, in turn, the quality of both biological and clinical measurements. High quality recombinant immunoreagents are generated using antibody-phage display. One metric of antibody quality – the binding affinity – is quantified through the dissociation constant (KD) of each recombinant antibody and the target antigen. To characterize the KD of recombinant antibodies and target antigen, we introduce affinity electrophoretic mobility shift assays (EMSAs) in a high-throughput format suitable for small volume samples. A microfluidic card comprised of free-standing polyacrylamide gel (fsPAG) separation lanes supports 384 concurrent EMSAs in 30 s using a single power source. Sample is dispensed onto the microfluidic EMSA card by acoustic droplet ejection (ADE), which reduces EMSA variability compared to sample dispensing using manual or pin tools. The KD for each of a six-member fragment antigen-binding fragment library is reported using ~25-fold less sample mass and ~5-fold less time than conventional heterogeneous assays. Given the form factor and performance of this micro- and mesofluidic workflow, we have developed a sample-sparing, high-throughput, solution-phase alternative for biomolecular affinity characterization. PMID:28008969

Distinct dissociation kinetics between ion pairs: Solvent-coordinate free-energy landscape analysis.

PubMed

Yonetani, Yoshiteru

2015-07-28

Different ion pairs exhibit different dissociation kinetics; however, while the nature of this process is vital for understanding various molecular systems, the underlying mechanism remains unclear. In this study, to examine the origin of different kinetic rate constants for this process, molecular dynamics simulations were conducted for LiCl, NaCl, KCl, and CsCl in water. The results showed substantial differences in dissociation rate constant, following the trend kLiCl < kNaCl < kKCl < kCsCl. Analysis of the free-energy landscape with a solvent reaction coordinate and subsequent rate component analysis showed that the differences in these rate constants arose predominantly from the variation in solvent-state distribution between the ion pairs. The formation of a water-bridging configuration, in which the water molecule binds to an anion and a cation simultaneously, was identified as a key step in this process: water-bridge formation lowers the related dissociation free-energy barrier, thereby increasing the probability of ion-pair dissociation. Consequently, a higher probability of water-bridge formation leads to a higher ion-pair dissociation rate.

Ammonium and nitrite oxidation at nanomolar oxygen concentrations in oxygen minimum zone waters

PubMed Central

Bristow, Laura A.; Dalsgaard, Tage; Tiano, Laura; Mills, Daniel B.; Bertagnolli, Anthony D.; Wright, Jody J.; Hallam, Steven J.; Ulloa, Osvaldo; Canfield, Donald E.; Revsbech, Niels Peter; Thamdrup, Bo

2016-01-01

A major percentage of fixed nitrogen (N) loss in the oceans occurs within nitrite-rich oxygen minimum zones (OMZs) via denitrification and anammox. It remains unclear to what extent ammonium and nitrite oxidation co-occur, either supplying or competing for substrates involved in nitrogen loss in the OMZ core. Assessment of the oxygen (O2) sensitivity of these processes down to the O2 concentrations present in the OMZ core (<10 nmol⋅L−1) is therefore essential for understanding and modeling nitrogen loss in OMZs. We determined rates of ammonium and nitrite oxidation in the seasonal OMZ off Concepcion, Chile at manipulated O2 levels between 5 nmol⋅L−1 and 20 μmol⋅L−1. Rates of both processes were detectable in the low nanomolar range (5–33 nmol⋅L−1 O2), but demonstrated a strong dependence on O2 concentrations with apparent half-saturation constants (Kms) of 333 ± 130 nmol⋅L−1 O2 for ammonium oxidation and 778 ± 168 nmol⋅L−1 O2 for nitrite oxidation assuming one-component Michaelis–Menten kinetics. Nitrite oxidation rates, however, were better described with a two-component Michaelis–Menten model, indicating a high-affinity component with a Km of just a few nanomolar. As the communities of ammonium and nitrite oxidizers were similar to other OMZs, these kinetics should apply across OMZ systems. The high O2 affinities imply that ammonium and nitrite oxidation can occur within the OMZ core whenever O2 is supplied, for example, by episodic intrusions. These processes therefore compete with anammox and denitrification for ammonium and nitrite, thereby exerting an important control over nitrogen loss. PMID:27601665

Direct simulation with vibration-dissociation coupling

NASA Technical Reports Server (NTRS)

Hash, David B.; Hassan, H. A.

1992-01-01

The majority of implementations of the Direct Simulation Monte Carlo (DSMC) method of Bird do not account for vibration-dissociation coupling. Haas and Boyd have proposed the vibrationally-favored dissociation model to accomplish this task. This model requires measurements of induction distance to determine model constants. A more general expression has been derived that does not require any experimental input. The model is used to calculate one-dimensional shock waves in nitrogen and the flow past a lunar transfer vehicle (LTV). For the conditions considered in the simulation, the influence of vibration-dissociation coupling on heat transfer in the stagnation region of the LTV can be significant.

A rigorous multiple independent binding site model for determining cell-based equilibrium dissociation constants.

PubMed

Drake, Andrew W; Klakamp, Scott L

2007-01-10

A new 4-parameter nonlinear equation based on the standard multiple independent binding site model (MIBS) is presented for fitting cell-based ligand titration data in order to calculate the ligand/cell receptor equilibrium dissociation constant and the number of receptors/cell. The most commonly used linear (Scatchard Plot) or nonlinear 2-parameter model (a single binding site model found in commercial programs like Prism(R)) used for analysis of ligand/receptor binding data assumes only the K(D) influences the shape of the titration curve. We demonstrate using simulated data sets that, depending upon the cell surface receptor expression level, the number of cells titrated, and the magnitude of the K(D) being measured, this assumption of always being under K(D)-controlled conditions can be erroneous and can lead to unreliable estimates for the binding parameters. We also compare and contrast the fitting of simulated data sets to the commonly used cell-based binding equation versus our more rigorous 4-parameter nonlinear MIBS model. It is shown through these simulations that the new 4-parameter MIBS model, when used for cell-based titrations under optimal conditions, yields highly accurate estimates of all binding parameters and hence should be the preferred model to fit cell-based experimental nonlinear titration data.

Determination of the dissociation constants (pKa) of secondary and tertiary amines in organic media by capillary electrophoresis and their role in the electrophoretic mobility order inversion.

PubMed

Cantu, Marcelo Delmar; Hillebranda, Sandro; Carrilho, Emanuel

2005-03-11

Non-aqueous capillary electrophoresis (NACE) may provide a selectivity enhancement in separations since the analyte dissociation constants (pKa) in organic media are different from those in aqueous solutions. In this work, we have studied the inversion in mobility order observed in the separation of tertiary (imipramine (IMI) and amitryptiline (AMI)) and secondary amines (desipramine (DES) and nortryptiline (NOR)) in water, methanol, and acetonitrile. We have determined the pKa values in those solvents and the variation of dissociation constants with the temperature. From these data, and applying the Van't Hoff equation, we have calculated the thermodynamic parameters deltaH and deltaS. The pKa values found in methanol for DES, NOR, IMI, and AMI were 10.80, 10.79, 10.38, and 10.33, respectively. On the other hand, in acetonitrile an opposite relation was found since the values were 20.60, 20.67, 20.74, and 20.81 for DES, NOR, IMI, and AMI. This is the reason why a migration order inversion is observed in NACE for these solvents. The thermodynamic parameters were evaluated and presented a tendency that can be correlated with that observed for pKa values.

Diarylpyrimidine-dihydrobenzyloxopyrimidine hybrids: new, wide-spectrum anti-HIV-1 agents active at (sub)-nanomolar level.

PubMed

Rotili, Dante; Tarantino, Domenico; Artico, Marino; Nawrozkij, Maxim B; Gonzalez-Ortega, Emmanuel; Clotet, Bonaventura; Samuele, Alberta; Esté, José A; Maga, Giovanni; Mai, Antonello

2011-04-28

Here, we describe a novel small series of non-nucleoside reverse transcriptase inhibitors (NNRTIs) that combine peculiar structural features of diarylpyrimidines (DAPYs) and dihydro-alkoxy-benzyl-oxopyrimidines (DABOs). These DAPY-DABO hybrids (1-4) showed a characteristic SAR profile and a nanomolar anti-HIV-1 activity at both enzymatic and cellular level. In particular, the two compounds 4d and 2d, with a (sub)nanomolar activity against wild-type and clinically relevant HIV-1 mutant strains, were selected as lead compounds for next optimization studies.

Determine equilibrium dissociation constant of drug-membrane receptor affinity using the cell membrane chromatography relative standard method.

PubMed

Ma, Weina; Yang, Liu; Lv, Yanni; Fu, Jia; Zhang, Yanmin; He, Langchong

2017-06-23

The equilibrium dissociation constant (K D ) of drug-membrane receptor affinity is the basic parameter that reflects the strength of interaction. The cell membrane chromatography (CMC) method is an effective technique to study the characteristics of drug-membrane receptor affinity. In this study, the K D value of CMC relative standard method for the determination of drug-membrane receptor affinity was established to analyze the relative K D values of drugs binding to the membrane receptors (Epidermal growth factor receptor and angiotensin II receptor). The K D values obtained by the CMC relative standard method had a strong correlation with those obtained by the frontal analysis method. Additionally, the K D values obtained by CMC relative standard method correlated with pharmacological activity of the drug being evaluated. The CMC relative standard method is a convenient and effective method to evaluate drug-membrane receptor affinity. Copyright © 2017 Elsevier B.V. All rights reserved.

Hit-Validation Methodologies for Ligands Isolated from DNA-Encoded Chemical Libraries.

PubMed

Zimmermann, Gunther; Li, Yizhou; Rieder, Ulrike; Mattarella, Martin; Neri, Dario; Scheuermann, Jörg

2017-05-04

DNA-encoded chemical libraries (DECLs) are large collections of compounds linked to DNA fragments, serving as amplifiable barcodes, which can be screened on target proteins of interest. In typical DECL selections, preferential binders are identified by high-throughput DNA sequencing, by comparing their frequency before and after the affinity capture step. Hits identified in this procedure need to be confirmed, by resynthesis and by performing affinity measurements. In this article we present new methods based on hybridization of oligonucleotide conjugates with fluorescently labeled complementary oligonucleotides; these facilitate the determination of affinity constants and kinetic dissociation constants. The experimental procedures were demonstrated with acetazolamide, a binder to carbonic anhydrase IX with a dissociation constant in the nanomolar range. The detection of binding events was compatible not only with fluorescence polarization methodologies, but also with Alphascreen technology and with microscale thermophoresis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rate constants for proteins binding to substrates with multiple binding sites using a generalized forward flux sampling expression

NASA Astrophysics Data System (ADS)

Vijaykumar, Adithya; ten Wolde, Pieter Rein; Bolhuis, Peter G.

2018-03-01

To predict the response of a biochemical system, knowledge of the intrinsic and effective rate constants of proteins is crucial. The experimentally accessible effective rate constant for association can be decomposed in a diffusion-limited rate at which proteins come into contact and an intrinsic association rate at which the proteins in contact truly bind. Reversely, when dissociating, bound proteins first separate into a contact pair with an intrinsic dissociation rate, before moving away by diffusion. While microscopic expressions exist that enable the calculation of the intrinsic and effective rate constants by conducting a single rare event simulation of the protein dissociation reaction, these expressions are only valid when the substrate has just one binding site. If the substrate has multiple binding sites, a bound enzyme can, besides dissociating into the bulk, also hop to another binding site. Calculating transition rate constants between multiple states with forward flux sampling requires a generalized rate expression. We present this expression here and use it to derive explicit expressions for all intrinsic and effective rate constants involving binding to multiple states, including rebinding. We illustrate our approach by computing the intrinsic and effective association, dissociation, and hopping rate constants for a system in which a patchy particle model enzyme binds to a substrate with two binding sites. We find that these rate constants increase as a function of the rotational diffusion constant of the particles. The hopping rate constant decreases as a function of the distance between the binding sites. Finally, we find that blocking one of the binding sites enhances both association and dissociation rate constants. Our approach and results are important for understanding and modeling association reactions in enzyme-substrate systems and other patchy particle systems and open the way for large multiscale simulations of such systems.

Predicting both passive intestinal absorption and the dissociation constant toward albumin using the PAMPA technique.

PubMed

Bujard, Alban; Sol, Marine; Carrupt, Pierre-Alain; Martel, Sophie

2014-10-15

The parallel artificial membrane permeability assay (PAMPA) is a high-throughput screening (HTS) method that is widely used to predict in vivo passive permeability through biological barriers, such as the skin, the blood brain barrier (BBB) and the gastrointestinal tract (GIT). The PAMPA technique has also been used to predict the dissociation constant (Kd) between a compound and human serum albumin (HSA) while disregarding passive permeability. Furthermore, the assay is based on the use of two separate 5-point kinetic experiments, which increases the analysis time. In the present study, we adapted the hexadecane membrane (HDM)-PAMPA assay to both predict passive gastrointestinal absorption via the permeability coefficient logPe value and determine the Kd. Two assays were performed: one in the presence and one in the absence of HSA in the acceptor compartment. In the absence of HSA, logPe values were determined after a 4-h incubation time, as originally described, but the dimethylsulfoxide (DMSO) percentage and pH were altered to be compatible with the protein. In parallel, a second PAMPA assay was performed in the presence of HSA during a 16-h incubation period. By adding HSA, a variation in the amount of compound crossing the membrane was observed compared to the permeability measured in the absence of HSA. The concentration of compound reaching the acceptor compartment in each case was used to determine both parameters (logPe and logKd) using numerical simulations, which highlighted the originality of this method because these calculations required only two endpoint measurements instead of a complete kinetic study. It should be noted that the amount of compound that reaches the acceptor compartment in the presence of HSA is modulated by complex dissociation in the receptor compartment. Only compounds that are moderately bound to albumin (-3

Tandem mass spectrometry of large biomolecule ions by blackbody infrared radiative dissociation.

PubMed

Price, W D; Schnier, P D; Williams, E R

1996-03-01

A new method for the dissociation of large ions formed by electrospray ionization is demonstrated. Ions trapped in a Fourier transform mass spectrometer at pressures below 10(-)(8) Torr are dissociated by elevating the vacuum chamber to temperatures up to 215 °C. Rate constants for dissociation are measured and found to be independent of pressure below 10(-)(7) Torr. This indicates that the ions are activated by absorption of blackbody radiation emitted from the chamber walls. Dissociation efficiencies as high as 100% are obtained. There is no apparent mass limit to this method; ions as large as ubiquitin (8.6 kDa) are readily dissociated. Thermally stable ions, such as melittin 3+ (2.8 kDa), did not dissociate at temperatures up to 200 °C. This method is highly selective for low-energy fragmentation, from which limited sequence information can be obtained. From the temperature dependence of the dissociation rate constants, Arrhenius activation energies in the low-pressure limit are obtained. The lowest energy dissociation processes for the singly and doubly protonated ions of bradykinin are loss of NH(3) and formation of the b(2)/y(7) complementary pair, with activation energies of 1.3 and 0.8 eV, respectively. No loss of NH(3) is observed for the doubly protonated ion; some loss of H(2)O occurs. These results show that charge-charge interactions not only lower the activation energy for dissociation but also can dramatically change the fragmentation, most likely through changes in the gas-phase conformation of the ion. Dissociation of ubiquitin ions produces fragmentation similar to that obtained by IRMPD and SORI-CAD. Higher charge state ions dissociate to produce y and b ions; the primary fragmentation process for low charge state ions is loss of H(2)O.

Dissociation behavior of methane--ethane mixed gas hydrate coexisting structures I and II.

PubMed

Kida, Masato; Jin, Yusuke; Takahashi, Nobuo; Nagao, Jiro; Narita, Hideo

2010-09-09

Dissociation behavior of methane-ethane mixed gas hydrate coexisting structures I and II at constant temperatures less than 223 K was studied with use of powder X-ray diffraction and solid-state (13)C NMR techniques. The diffraction patterns at temperatures less than 203 K showed both structures I and II simultaneously convert to Ih during the dissociation, but the diffraction pattern at temperatures greater than 208 K showed different dissociation behavior between structures I and II. Although the diffraction peaks from structure II decreased during measurement at constant temperatures greater than 208 K, those from structure I increased at the initial step of dissociation and then disappeared. This anomalous behavior of the methane-ethane mixed gas hydrate coexisting structures I and II was examined by using the (13)C NMR technique. The (13)C NMR spectra revealed that the anomalous behavior results from the formation of ethane-rich structure I. The structure I hydrate formation was associated with the dissociation rate of the initial methane-ethane mixed gas hydrate.

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.

Mechanism of action of a nanomolar potent, allosteric antagonist of the thyroid-stimulating hormone receptor

PubMed Central

van Koppen, Chris J; de Gooyer, Marcel E; Karstens, Willem-Jan; Plate, Ralf; Conti, Paolo GM; van Achterberg, Tanja AE; van Amstel, Monique GA; Brands, Jolanda HGM; Wat, Jesse; Berg, Rob JW; Lane, J Robert D; Miltenburg, Andre MM; Timmers, C Marco

2012-01-01

BACKGROUND AND PURPOSE Graves' disease (GD) is an autoimmune disease in which the thyroid is overactive, producing excessive amounts of thyroid hormones, caused by thyroid-stimulating hormone (TSH) receptor-stimulating immunoglobulins (TSIs). Many GD patients also suffer from thyroid eye disease (Graves' ophthalmopathy or GO), as TSIs also activate TSH receptors in orbital tissue. We recently developed low molecular weight (LMW) TSH receptor antagonists as a novel therapeutic strategy for the treatment of GD and GO. Here, we determined the molecular pharmacology of a prototypic, nanomolar potent LMW TSH receptor antagonist, Org 274179-0. EXPERIMENTAL APPROACH Using CHO cells heterogeneously expressing human TSH receptors and rat FRTL-5 cells endogenously expressing rat TSH receptors, we determined the potency and efficacy of Org 274179-0 at antagonizing TSH- and TSI-induced TSH receptor signalling and its cross-reactivity at related follicle-stimulating hormone and luteinizing hormone receptors. We analysed the allosteric mode of interaction of Org 274179-0 and determined whether it is an inverse agonist at five naturally occurring, constitutively active TSH receptor mutants. KEY RESULTS Nanomolar concentrations of Org 274179-0 completely inhibited TSH (and TSI)-mediated TSH receptor activation with little effect on the potency of TSH, in accordance with an allosteric mechanism of action. Conversely, increasing levels of TSH receptor stimulation only marginally reduced the antagonist potency of Org 274179-0. Org 274179-0 fully blocked the increased basal activity of all the constitutively active TSH receptor mutants tested with nanomolar potencies. CONCLUSIONS AND IMPLICATIONS Nanomolar potent TSH receptor antagonists like Org 274179-0 have therapeutic potential for the treatment of GD and GO. PMID:22014107

Temperature Dependence of Dissociative Electron Attachment to Halogenated Hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Yicheng; Christophorou, Loucas G.

1996-10-01

Most of the gas mixtures currently in use for plasma processing of semiconductors involve halogenated hydrocarbons such as the strongly electronegative gases CCl4 and CFCl_3, the weakly electronegative gas CF_2Cl2 and the very weakly electronegative gases CHF3 and CF_4. Many dissociation processes are known to occur for these molecules. One of these dissociation reactions which is particularly effective for the strongly electronegative hydrocarbons is dissociative electron attachment. Even for weakly electron attaching gases, molecular dissociation via dissociative electron attachment at low energies can be an efficient dissociation process if the gas temperature is higher than ambient. Dissociative electron attachment is known to increase with increasing temperature above room temperature for many such compounds. In this paper, we report our measurements on the increases of the total electron attachment rate constant for CF_2Cl2 with increasing gas temperature from room temperature to about 600 K. -Research sponsored in part by the U.S. Air Force Wright Laboratory under contract F33615-96-C-2600 with the University of Tennessee. Also, Department of Physics, The University of Tennessee, Knoxville, TN.

Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.

PubMed

Uddin, M; Coombe, D

2014-03-20

Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to

Force and Stress along Simulated Dissociation Pathways of Cucurbituril-Guest Systems.

PubMed

Velez-Vega, Camilo; Gilson, Michael K

2012-03-13

The field of host-guest chemistry provides computationally tractable yet informative model systems for biomolecular recognition. We applied molecular dynamics simulations to study the forces and mechanical stresses associated with forced dissociation of aqueous cucurbituril-guest complexes with high binding affinities. First, the unbinding transitions were modeled with constant velocity pulling (steered dynamics) and a soft spring constant, to model atomic force microscopy (AFM) experiments. The computed length-force profiles yield rupture forces in good agreement with available measurements. We also used steered dynamics with high spring constants to generate paths characterized by a tight control over the specified pulling distance; these paths were then equilibrated via umbrella sampling simulations and used to compute time-averaged mechanical stresses along the dissociation pathways. The stress calculations proved to be informative regarding the key interactions determining the length-force profiles and rupture forces. In particular, the unbinding transition of one complex is found to be a stepwise process, which is initially dominated by electrostatic interactions between the guest's ammoniums and the host's carbonyl groups, and subsequently limited by the extraction of the guest's bulky bicyclooctane moiety; the latter step requires some bond stretching at the cucurbituril's extraction portal. Conversely, the dissociation of a second complex with a more slender guest is mainly driven by successive electrostatic interactions between the different guest's ammoniums and the host's carbonyl groups. The calculations also provide information on the origins of thermodynamic irreversibilities in these forced dissociation processes.

A nonaqueous potentiometric titration study of the dissociation of t-butyl methacrylate-methacrylic acid copolymers.

PubMed

Nakatani, Kiyoharu; Yamashita, Jun; Sekine, Tomomi; Toriumi, Minoru; Itani, Toshiro

2003-05-01

The dissociation of t-butyl methacrylate-methacrylic acid copolymers in dimethyl sulfoxide was analyzed by a nonaqueous potentiometric titration technique. The negative logarithm of the dissociation constant of the monomer unit of a methacrylic acid (MAA) monotonously increased with the increasing degree of dissociation corresponding to the titrant/MAA amount ratio, and was highly influenced by the copolymerization ratio. The results are discussed in terms of the suppression of the dissociation of MAA by a neighboring charged methacrylate anion unit.

In vitro analysis of human immunodeficiency virus particle dissociation: gag proteolytic processing influences dissociation kinetics.

PubMed

Müller, Barbara; Anders, Maria; Reinstein, Jochen

2014-01-01

Human immunodeficiency virus particles undergo a step of proteolytic maturation, in which the main structural polyprotein Gag is cleaved into its mature subunits matrix (MA), capsid (CA), nucleocapsid (NC) and p6. Gag proteolytic processing is accompanied by a dramatic structural rearrangement within the virion, which is necessary for virus infectivity and has been proposed to proceed through a sequence of dissociation and reformation of the capsid lattice. Morphological maturation appears to be tightly regulated, with sequential cleavage events and two small spacer peptides within Gag playing important roles by regulating the disassembly of the immature capsid layer and formation of the mature capsid lattice. In order to measure the influence of individual Gag domains on lattice stability, we established Förster's resonance energy transfer (FRET) reporter virions and employed rapid kinetic FRET and light scatter measurements. This approach allowed us to measure dissociation properties of HIV-1 particles assembled in eukaryotic cells containing Gag proteins in different states of proteolytic processing. While the complex dissociation behavior of the particles prevented an assignment of kinetic rate constants to individual dissociation steps, our analyses revealed characteristic differences in the dissociation properties of the MA layer dependent on the presence of additional domains. The most striking effect observed here was a pronounced stabilization of the MA-CA layer mediated by the presence of the 14 amino acid long spacer peptide SP1 at the CA C-terminus, underlining the crucial role of this peptide for the resolution of the immature particle architecture.

Subunit dissociation in fish hemoglobins.

PubMed

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

1976-12-10

solutions containing guanidine hydrochloride indicated that there are changes in both the absolute rates and the proportions of the fast and slow components, which along with other factors complicated the analysis of the data in terms of dissociation constants. Measurements were also made in solutions containing urea to promote dissociation, but with this agent very high concentrations (about 6 M) were required to give measureable dissociation and the fish hemoglobins were unstable under these conditions, with appreciable loss of absorbance spectra in both the sedimentation and kinetic experiments.

Dissociation of Heme–Globin Complexes by Blackbody Infrared Radiative Dissociation: Molecular Specificity in the Gas Phase?

PubMed Central

Gross, Deborah S.; Zhao, Yuexing; Williams, Evan R.

2005-01-01

The temperature dependence of the unimolecular kinetics for dissociation of the heme group from holo-myoglobin (Mb) and holo-hemoglobin α-chain (Hb-α) was investigated with blackbody infrared radiative dissociation (BIRD). The rate constant for dissociation of the 9 + charge state of Mb formed by electrospray ionization from a “pseudo-native” solution is 60% lower than that of Hb-α at each of the temperatures investigated. In solutions of pH 5.5–8.0, the thermal dissociation rate for Mb is also lower than that of HB-α (Hargrove, M. S. et al. J. Biol. Chem. 1994, 269, 4207–4214). Thus, Mb is thermally more stable with respect to heme loss than Hb-α both in the gas phase and in solution. The Arrhenius activation parameters for both dissociation processes are indistinguishable within the current experimental error (activation energy 0.9 eV and pre-exponential factor of 108–10 s−1). The 9+ to 12+ charge states of Mb have similar Arrhenius parameters when these ions are formed from pseudo-native solutions. In contrast, the activation energies and pre-exponential factors decrease from 0.8 to 0.3 eV and 107 to 102 s−1, respectively, for the 9 + to 12 + charge states formed from acidified solutions in which at least 50% of the secondary structure is lost. These results demonstrate that gas-phase Mb ions retain clear memory of the composition of the solution from which they are formed and that these differences can be probed by BIRD. PMID:16479269

Dissociation of heme-globin complexes by blackbody infrared radiative dissociation: molecular specificity in the gas phase?

PubMed

Gross, D S; Zhao, Y; Williams, E R

1997-05-01

The temperature dependence of the unimolecular kinetics for dissociation of the heme group from holo-myoglobin (Mb) and holo-hemoglobin alpha-chain (Hb-alpha) was investigated with blackbody infrared radiative dissociation (BIRD). The rate constant for dissociation of the 9 + charge state of Mb formed by electrospray ionization from a "pseudo-native" solution is 60% lower than that of Hb-alpha at each of the temperatures investigated. In solutions of pH 5.5-8.0, the thermal dissociation rate for Mb is also lower than that of HB-alpha (Hargrove, M. S. et al. J. Biol. Chem.1994, 269, 4207-4214). Thus, Mb is thermally more stable with respect to heme loss than Hb-alpha both in the gas phase and in solution. The Arrhenius activation parameters for both dissociation processes are indistinguishable within the current experimental error (activation energy 0.9 eV and pre-exponential factor of 10(8-10) s(-1)). The 9+ to 12+ charge states of Mb have similar Arrhenius parameters when these ions are formed from pseudo-native solutions. In contrast, the activation energies and pre-exponential factors decrease from 0.8 to 0.3 eV and 10(7) to 10(2) s(-1), respectively, for the 9 + to 12 + charge states formed from acidified solutions in which at least 50% of the secondary structure is lost. These results demonstrate that gas-phase Mb ions retain clear memory of the composition of the solution from which they are formed and that these differences can be probed by BIRD.

A Theoretical Basis for the Transition to Denitrification at Nanomolar Oxygen Concentrations

NASA Astrophysics Data System (ADS)

Zakem, E.; Follows, M. J.

2016-02-01

Current climate change is likely to expand the size and intensity of marine oxygen minimum zones. How will this affect denitrification rates? Current global biogeochemical models typically prescribe a critical oxygen concentration below which anaerobic activity occurs, rather than resolve the underlying microbial processes. Here, we explore the dynamics of an idealized, simulated anoxic zone in which multiple prokaryotic metabolisms are resolved mechanistically, defined by redox chemistry and biophysical constraints. We first ask, what controls the critical oxygen concentration governing the favorability of aerobic or anaerobic respiration? The predicted threshold oxygen concentration varies as a function of the environment as well as of cell physiology, and lies within the nanomolar range. The model thus provides a theoretical underpinning for the recent observations of nanomolar oxygen concentrations in oxygen minimum zones. In the context of an idealized, two-dimensional intensified upwelling simulation, we also predict denitrification at oxygen concentrations orders of magnitude higher due to physical mixing, reconciling observations of denitrification over a similar range and demonstrating a decoupling of denitrification from the local oxygen concentration. In a sensitivity study with the idealized ocean model, we comment upon the relationship between the volume of anoxic waters and total denitrification.

The 6300 A O/1-D/ airglow and dissociative recombination

NASA Technical Reports Server (NTRS)

Wickwar, V. B.; Cogger, L. L.; Carlson, H. C.

1974-01-01

Measurements of night-time 6300 A airglow intensities at the Arecibo Observatory have been compared with dissociative recombination calculations based on electron densities derived from simultaneous incoherent backscatter measurements. The agreement indicates that the nightglow can be fully accounted for by dissociative recombination. The comparisons are examined to determine the importance of quenching, heavy ions, ionization above the F-layer peak, and the temperature parameter of the model atmosphere. Comparable fits between the observed and calculated intensities are found for several available model atmospheres. The least-squares fitting process, used to make the comparisons, produces comparable fits over a wide range of combinations of neutral densities and of reaction constants. Yet, the fitting places constraints upon the possible combinations; these constraints indicate that the latest laboratory chemical constants and densities extrapolated to a base altitude are mutually consistent.

Psychiatric symptoms and dissociation in conversion, somatization and dissociative disorders.

PubMed

Espirito-Santo, Helena; Pio-Abreu, Jose Luis

2009-03-01

Conversion, dissociation and somatization are historically related in the long established concept of hysteria. Somewhere along the way they were separated due to the Cartesian dualistic view. The aim of the present study was to compare these pathologies and investigate whether symptoms of these pathologies overlap in their clinical appearance in a Portuguese sample. Twenty-six patients with conversion disorder, 38 with dissociative disorders, 40 with somatization disorder, and a comparison group of 46 patients having other psychiatric disorders answered questions about dissociation (Dissociative Experiences Scale), somatoform dissociation (Somatoform Dissociation Questionnaire), and psychopathological symptoms (Brief Symptom Inventory). Dissociative and somatoform symptoms were significantly more frequent in dissociative and conversion disorder than in somatization disorder and controls. There were no significant differences between dissociative and conversion patients. Conversion disorder is closely related to dissociative disorders. These results support the ICD-10 categorization of conversion disorder among dissociative disorders and the hypothesis of analogous psychopathological processes in conversion and dissociative disorders versus somatization disorder.

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.

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.

Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

PubMed Central

Bao, Junwei Lucas; Zhang, Xin

2016-01-01

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727

Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice-Ramsperger-Kassel theory.

PubMed

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

2016-11-29

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C 2 F 4 ), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice-Ramsperger-Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements.

Molecular dynamics simulation of low dielectric constant polymer electrolytes

NASA Astrophysics Data System (ADS)

Wheatle, Bill; Lynd, Nathaniel; Ganesan, Venkat

Recent experimental studies measured the ionic conductivities of a series of poly(glycidyl ether)s with varying neat dielectric constants (ɛ), viscosities (η), and glass transition temperatures (Tg), as hosts for lithium bistrifluoromethanesulfonimide (LiTFSI) salt. In such a context, it was demonstrated that the ionic conductivity of these polymer electrolytes was a function of ɛ rather than Tg or η, suggesting that there may exist regimes in which ionic conductivity is not limited by slow segmental dynamics but rather by low ionic dissociation. Motivated by such results, we used atomistic molecular dynamics to study the structure and transport characteristics of the same set of host polymers. We found that the coordination number of TFSI- about Li+ in the first solvation shell and the total fraction of free ions increased as a function of ɛ, implying the polymer hosts enhanced ion dissociation. In addition, we found that increasing the dielectric constant of the host polymer enhanced self-correlated ion transport, as evidenced by an increase in the diffusion coefficients of each ion species. Overall, we confirmed that limited ion dissociation in low- ɛ polymer electrolyte hosts hampers ionic conductivity. We would like to thank the National Science Foundation Graduate Research Fellowship Program for funding this research endeavor.

Quantitative analysis of the interactions between prenyl Rab9, GDP dissociation inhibitor-alpha, and guanine nucleotides.

PubMed

Shapiro, A D; Pfeffer, S R

1995-05-12

Rab9 is a Ras-like GTPase required for the transport of mannose 6-phosphate receptors between late endosomes and the trans Golgi network. Rab9 occurs in the cytosol as a complex with GDP dissociation inhibitor (GDI), which we have shown delivers prenyl Rab9 to late endosomes in a functional form. We report here basal rate constants for guanine nucleotide dissociation and GTP hydrolysis for prenyl Rab9. Both rate constants were influenced in part by the hydrophobic environment of the prenyl group. Guanine nucleotide dissociation and GTP hydrolysis rates were lower in the presence of lipid; detergent stimulated intrinsic nucleotide exchange. GDI-alpha inhibited GDP dissociation from prenyl Rab9 by 2.4-fold. GDI-alpha associated with prenyl Rab9 with a KD of 60 nM in 0.1% Lubrol and 23 nM in 0.02% Lubrol. In 0.1% Lubrol, GDI-alpha inhibited GDP dissociation half maximally at 72 +/- 18 nM, consistent with the KD determinations. These data suggest that GDI-alpha associates with prenyl Rab9 with a KD of < or = 23 nM under physiological conditions. Finally, a previously uncharacterized minor form of GDI-alpha inhibited GDP dissociation from prenyl Rab9 by 1.9-fold and bound prenyl Rab9 with a KD of 67 nM in 0.1% Lubrol.

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. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Ab Initio Calculations of the N-N Bond Dissociation for the Gas-phase RDX and HMX.

PubMed

Liu, Lin-Lin; Liu, Pei-Jin; Hu, Song-Qi; He, Guo-Qiang

2017-01-17

NO 2 fission is a vital factor for 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) decomposition. In this study, the geometry of the gas-phase RDX and HMX molecules was optimized, and the bond order and the bond dissociation energy of the N-N bonds were examined. Moreover, the rate constants of the gas-phase RDX and HMX conformers, concerning the N-N bond dissociation, were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that HMX is more stable than RDX in terms of the N-N bond dissociation, and the conformers stability parameters were as follows: RDXaaa < RDXaae < HMX I < HMX II. In addition, for the RDX conformers, the N-N bond of the pseudo-equatorial positioning of the nitro group was more stable than the N-N bond of the axial positioning of the nitro group, while the results were opposite in the case of the HMX conformers. Moreover, it has been shown that the dissociation rate constant of the N-N bond is influenced by the temperature significantly, thus the rate constants were much lower (<10 -10  s -1 ) when the temperature was less than 1000 K.

Ab Initio Calculations of the N-N Bond Dissociation for the Gas-phase RDX and HMX

PubMed Central

Liu, Lin-lin; Liu, Pei-jin; Hu, Song-qi; He, Guo-qiang

2017-01-01

NO2 fission is a vital factor for 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) decomposition. In this study, the geometry of the gas-phase RDX and HMX molecules was optimized, and the bond order and the bond dissociation energy of the N-N bonds were examined. Moreover, the rate constants of the gas-phase RDX and HMX conformers, concerning the N-N bond dissociation, were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that HMX is more stable than RDX in terms of the N-N bond dissociation, and the conformers stability parameters were as follows: RDXaaa < RDXaae < HMX I < HMX II. In addition, for the RDX conformers, the N-N bond of the pseudo-equatorial positioning of the nitro group was more stable than the N-N bond of the axial positioning of the nitro group, while the results were opposite in the case of the HMX conformers. Moreover, it has been shown that the dissociation rate constant of the N-N bond is influenced by the temperature significantly, thus the rate constants were much lower (<10−10 s−1) when the temperature was less than 1000 K. PMID:28094774

Ab Initio Calculations of the N-N Bond Dissociation for the Gas-phase RDX and HMX

NASA Astrophysics Data System (ADS)

Liu, Lin-Lin; Liu, Pei-Jin; Hu, Song-Qi; He, Guo-Qiang

2017-01-01

NO2 fission is a vital factor for 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) decomposition. In this study, the geometry of the gas-phase RDX and HMX molecules was optimized, and the bond order and the bond dissociation energy of the N-N bonds were examined. Moreover, the rate constants of the gas-phase RDX and HMX conformers, concerning the N-N bond dissociation, were evaluated using the microcanonical variational transition state theory (μVT). The calculation results have shown that HMX is more stable than RDX in terms of the N-N bond dissociation, and the conformers stability parameters were as follows: RDXaaa < RDXaae < HMX I < HMX II. In addition, for the RDX conformers, the N-N bond of the pseudo-equatorial positioning of the nitro group was more stable than the N-N bond of the axial positioning of the nitro group, while the results were opposite in the case of the HMX conformers. Moreover, it has been shown that the dissociation rate constant of the N-N bond is influenced by the temperature significantly, thus the rate constants were much lower (<10-10 s-1) when the temperature was less than 1000 K.

Blackbody infrared radiative dissociation of protonated oligosaccharides.

PubMed

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 (Cel(6)), which is composed of β-(1→4)-linked glucopyranose rings, and five malto-oligosaccharides (Mal(x), 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 (B(1) and B(2)) also occurs. Rate constants for dissociation of the protonated oligosaccharides and the corresponding Arrhenius activation parameters (E(a) and A) were determined. The E(a) and A-factors measured for protonated Mal(x) (x>4) are indistinguishable within error (~19 kcal mol(-1), 10(10) s(-1)), which is consistent with the ions being in the rapid energy exchange limit. In contrast, the Arrhenius parameters for protonated Cel(6) (24 kcal mol(-1), 10(12) 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. © American Society for Mass Spectrometry, 2011

Equations for calculating the properties of dissociated steam

NASA Astrophysics Data System (ADS)

Aminov, R. Z.; Gudym, A. A.

2017-08-01

The equations of state for dissociated steam have been developed in the temperature and pressure ranges of 1250-2300 K and 0.01-10.00 MPa for calculating thermodynamic processes in thermal power units operating on high-temperature steam. These equations are based on the property tables for dissociated steam derived at a reference temperature of 0 K. It is assumed that the initial substance is steam, the dissociation of which—in accordance with the most likely chemical reactions—results in formation of molecules of hydrogen, oxygen, steam, hydroxyl, and atoms of oxygen and hydrogen. Differential thermodynamic correlations, considering a change in the chemical potential and the composition of the mixture, during the steam dissociation are used. A reference temperature of 0.01°C used in the calculation of parameters of nondissociated steam has been adopted to predict processes in thermal power units without matching the reference temperatures and to account for transformation of dissociated steam into its usual form for which there is the international system of equations with the water triple point of 0.01°C taken as the reference. In the investigated region, the deviation of dissociated steam properties from those of nondissociated steam, which increases with decreasing the pressure or increasing the temperature, was determined. For a pressure of 0.02 MPa and a temperature of 2200 K, these deviations are 512 kJ/kg for the enthalpy, 0.2574 kJ/(kg K) for the entropy, and 3.431 kJ/(kg K) for the heat capacity at constant pressure. The maximum deviation of the dissociated steam properties calculated by the developed equations from the handbook values that these equations are based on does not exceed 0.03-0.05%.

The influence of porosity and structural parameters on different kinds of gas hydrate dissociation

PubMed Central

Misyura, S. Y.

2016-01-01

Methane hydrate dissociation at negative temperatures was studied experimentally for different artificial and natural samples, differing by macro- and micro-structural parameters. Four characteristic dissociation types are discussed in the paper. The internal kinetics of artificial granule gas hydrates and clathrate hydrates in coal is dependent on the porosity, defectiveness and gas filtration rate. The density of pores distribution in the crust of formed ice decreases by the several orders of magnitude and this change significantly the rate of decay. Existing models for describing dissociation at negative temperatures do not take into account the structural parameters of samples. The dissociation is regulated by internal physical processes that must be considered in the simulation. Non-isothermal dissociation with constant external heat flux was simulated numerically. The dissociation is simulated with consideration of heat and mass transfer, kinetics of phase transformation and gas filtering through a porous medium of granules for the negative temperatures. It is shown that the gas hydrate dissociation in the presence of mainly microporous structures is fundamentally different from the disintegration of gas hydrates containing meso and macropores. PMID:27445113

The lowest-lying electronic singlet and triplet potential energy surfaces for the HNO-NOH system: energetics, unimolecular rate constants, tunneling and kinetic isotope effects for the isomerization and dissociation reactions.

PubMed

Bozkaya, Uğur; Turney, Justin M; Yamaguchi, Yukio; Schaefer, Henry F

2012-04-28

The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO-NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the (1)HNO → (1)NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol(-1). For the barrierless decomposition of (1)HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol(-1). For (1)NOH → H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol(-1). On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol(-1) for the isomerization reaction (3)HNO → (3)NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol(-1). Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol(-1) for the dissociation reaction of (3)NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet-triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol(-1) for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to

LUMOS--A Sensitive and Reliable Optode System for Measuring Dissolved Oxygen in the Nanomolar Range.

PubMed

Lehner, Philipp; Larndorfer, Christoph; Garcia-Robledo, Emilio; Larsen, Morten; Borisov, Sergey M; Revsbech, Niels-Peter; Glud, Ronnie N; Canfield, Donald E; Klimant, Ingo

2015-01-01

Most commercially available optical oxygen sensors target the measuring range of 300 to 2 μmol L-1. However these are not suitable for investigating the nanomolar range which is relevant for many important environmental situations. We therefore developed a miniaturized phase fluorimeter based measurement system called the LUMOS (Luminescence Measuring Oxygen Sensor). It consists of a readout device and specialized "sensing chemistry" that relies on commercially available components. The sensor material is based on palladium(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin embedded in a Hyflon AD 60 polymer matrix and has a KSV of 6.25 x 10-3 ppmv-1. The applicable measurement range is from 1000 nM down to a detection limit of 0.5 nM. A second sensor material based on the platinum(II) analogue of the porphyrin is spectrally compatible with the readout device and has a measurement range of 20 μM down to 10 nM. The LUMOS device is a dedicated system optimized for a high signal to noise ratio, but in principle any phase flourimeter can be adapted to act as a readout device for the highly sensitive and robust sensing chemistry. Vise versa, the LUMOS fluorimeter can be used for read out of less sensitive optical oxygen sensors based on the same or similar indicator dyes, for example for monitoring oxygen at physiological conditions. The presented sensor system exhibits lower noise, higher resolution and higher sensitivity than the electrochemical STOX sensor previously used to measure nanomolar oxygen concentrations. Oxygen contamination in common sample containers has been investigated and microbial or enzymatic oxygen consumption at nanomolar concentrations is presented.

Dissociative electron attachment to C{sub 2}F{sub 5} radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haughey, Sean A.; Field, Thomas A.; Langer, Judith

Dissociative electron attachment to the reactive C{sub 2}F{sub 5} molecular radical has been investigated with two complimentary experimental methods; a single collision beam experiment and a new flowing afterglow Langmuir probe technique. The beam results show that F{sup -} is formed close to zero electron energy in dissociative electron attachment to C{sub 2}F{sub 5}. The afterglow measurements also show that F{sup -} is formed in collisions between electrons and C{sub 2}F{sub 5} molecules with rate constants of 3.7 Multiplication-Sign 10{sup -9} cm{sup 3} s{sup -1} to 4.7 Multiplication-Sign 10{sup -9} cm{sup 3} s{sup -1} at temperatures of 300-600 K. Themore » rate constant increases slowly with increasing temperature, but the rise observed is smaller than the experimental uncertainty of 35%.« less

Synthesis, crystal structure, DFT studies, acid dissociation constant, and antimicrobial activity of methyl 2-(4-chlorophenyl)-7a-((4-chlorophenyl)carbamothioyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate

NASA Astrophysics Data System (ADS)

Nural, Yahya; Gemili, Muge; Seferoglu, Nurgul; Sahin, Ertan; Ulger, Mahmut; Sari, Hayati

2018-05-01

A novel bicyclic thiohydantoin fused to pyrrolidine compound, methyl 2-(4-chlorophenyl)-7a-((4-chlorophenyl)carbamothioyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate, was synthesized by the cyclization reaction of dimethyl 5,5-diphenylpyrrolidine-2,4-dicarboxylate and 4-chlorophenyl isothiocyanate in the presence of 4-(dimethylamino)pyridine to form methyl 2-(4-chlorophenyl)-1-oxo-5,5-diphenyl-3-thioxo-hexahydro-1H-pyrrolo[1,2-e]imidazole-6-carboxylate with concomitant addition reaction of the 4-chlorophenyl isothiocyanate in 79% yield. The structural characterization was performed by NMR, FT-IR, MS and HRMS techniques, and the stereochemistry of the compound was determined by single crystal X-ray diffraction study. In addition, the molecular structure and 1H and 13C NMR chemical shifts of the compound were obtained with the density functional theory and Hartree-Fock calculations. Acid dissociation constants of the compound were determined using potentiometric titration method in 25% (v/v) dimethyl sulfoxide-water hydroorganic solvent at 25 ± 0.1 °C, at an ionic background of 0.1 mol/L of NaCl using the HYPERQUAD computer program. Four acid dissociation constants were obtained for the compound, and we suggest that these acid dissociation constants are related to the NH, for two groups of enthiols and enol groups. Antimicrobial activity study was performed against S. aureus, B. subtilis, A. hydrophila, E. coli and A. baumannii as bacterial standard strains, and against M. tuberculosis H37Rv as mycobacterial strain. The compound exhibited antibacterial activity in the range of 31.25-62.5 μg/mL, and antimycobacterial activity with a MIC value of 40 μg/mL against the indicated strains.

The effective temperature of Peptide ions dissociated by sustained off-resonance irradiation collisional activation in fourier transform mass spectrometry.

PubMed

Schnier, P D; Jurchen, J C; Williams, E R

1999-01-28

A method for determining the internal energy of biomolecule ions activated by collisions is demonstrated. The dissociation kinetics of protonated leucine enkephalin and doubly protonated bradykinin were measured using sustained off-resonance irradiation (SORI) collisionally activated dissociation (CAD) in a Fourier transform mass spectrometer. Dissociation rate constants are obtained from these kinetic data. In combination with Arrhenius parameters measured with blackbody infrared radiative dissociation, the "effective" temperatures of these ions are obtained. Effects of excitation voltage and frequency and the ion cell pressure were investigated. With typical SORI-CAD experimental conditions, the effective temperatures of these peptide ions range between 200 and 400 degrees C. Higher temperatures can be easily obtained for ions that require more internal energy to dissociate. The effective temperatures of both protonated leucine enkephalin and doubly protonated bradykinin measured with the same experimental conditions are similar. Effective temperatures for protonated leucine enkephalin can also be obtained from the branching ratio of the b(4) and (M + H - H(2)O)(+) pathways. Values obtained from this method are in good agreement with those obtained from the overall dissociation rate constants. Protonated leucine enkephalin is an excellent "thermometer" ion and should be well suited to establishing effective temperatures of ions activated by other dissociation techniques, such as infrared photodissociation, as well as ionization methods, such as matrix assisted laser desorption/ionization.

The Effective Temperature of Peptide Ions Dissociated by Sustained Off-Resonance Irradiation Collisional Activation in Fourier Transform Mass Spectrometry

PubMed Central

Schnier, Paul D.; Jurchen, John C.; Williams, Evan R.

2005-01-01

A method for determining the internal energy of biomolecule ions activated by collisions is demonstrated. The dissociation kinetics of protonated leucine enkephalin and doubly protonated bradykinin were measured using sustained off-resonance irradiation (SORI) collisionally activated dissociation (CAD) in a Fourier transform mass spectrometer. Dissociation rate constants are obtained from these kinetic data. In combination with Arrhenius parameters measured with blackbody infrared radiative dissociation, the “effective” temperatures of these ions are obtained. Effects of excitation voltage and frequency and the ion cell pressure were investigated. With typical SORI–CAD experimental conditions, the effective temperatures of these peptide ions range between 200 and 400 °C. Higher temperatures can be easily obtained for ions that require more internal energy to dissociate. The effective temperatures of both protonated leucine enkephalin and doubly protonated bradykinin measured with the same experimental conditions are similar. Effective temperatures for protonated leucine enkephalin can also be obtained from the branching ratio of the b4 and (M + H − H2O)+ pathways. Values obtained from this method are in good agreement with those obtained from the overall dissociation rate constants. Protonated leucine enkephalin is an excellent “thermometer” ion and should be well suited to establishing effective temperatures of ions activated by other dissociation techniques, such as infrared photodissociation, as well as ionization methods, such as matrix assisted laser desorption/ionization. PMID:16614752

The eΠ3g state of C2: A pathway to dissociation

NASA Astrophysics Data System (ADS)

Welsh, B. A.; Krechkivska, O.; Nauta, K.; Bacskay, G. B.; Kable, S. H.; Schmidt, T. W.

2017-07-01

The lowest 13 vibrational levels, v = 0-12, of the eΠ3g state of the C2 molecule have been measured by laser-induced fluorescence of new bands of the Fox-Herzberg system. The newly observed levels, v = 5-12, which span the eΠ3g electronic state up to and beyond the first dissociation threshold of C2, were analyzed to afford highly accurate molecular constants, including band origins, and rotational and spin-orbit constants. The spin-orbit coupling constants of the previously published lowest five levels are revised in sign and magnitude, requiring an overhaul of previously published molecular constants. The analysis is supported by high level ab initio calculations. Lifetimes of all observed levels were recorded and found to be in excellent agreement with ab initio predicted values up to v = 11. v = 12 was found to exhibit a much reduced lifetime and fluorescence quantum yield, which is attributed to the onset of predissociation. This brackets the dissociation energy of ground state XΣ+1g C2 between 6.1803 and 6.2553 eV, in agreement with the Active Thermochemical Tables.

Yeast hexokinase: substrate-induced association--dissociation reactions in the binding of glucose to hexokinase P-II.

PubMed

Hoggett, J G; Kellett, G L

1976-06-15

A method is described for the purification of native hexokinases P-I and P-II from yeast using preparative isoelectric focussing to separate the isozymes. The binding of glucose to hexokinase P-II, and the effect of this on the monomer--dimer association--dissociation reaction have been investigated quantitatively by a combination of titrations of intrinsic protein fluorescence and equilibrium ultracentrifugation. Association constants for the monomer-dimer reaction decreased with increasing pH, ionic strength and concentration of glucose. Saturating concentrations of glucose did not bring about complete dissociation of the enzyme showing that both sites were occupired in the dimer. At pH 8.0 and high ionic strength, where the enzyme existed as monomer, the dissociation constant of the enzyme-glucose complex was 3 X 10(-4) mol 1(-1) and was independent of the concentration of enzyme. Binding to the dimeric form at low pH and ionic strength (I=0.02 mol 1(-1), pH less than 7.5) was also independent of enzyme concentration (in the range 10-1000 mug ml-1) but was much weaker. The process could be described by a single dissociation constant, showing that the two available sites on the dimer were equivalent and non-cooperative; values of the intrinsic dissociation constant varied from 2.5 X 10(-3) mol 1(-1) at pH 7.0 to 6 X 10(-3) at pH 6.5. Under intermediate conditions (pH 7.0, ionic strength=0.15 mol 1(-1)), where monomer and dimer coexisted, the binding of glucose showed weak positive cooperatively (Hill coefficient 1.2); in addition, the binding was dependent upon the concentration of enzyme in the direction of stronger binding at lower concentrations. The results show that the phenomenon of half-sites reactivity observed in the binding of glucose to crystalline hexokinase P-II does not occur in solution; the simplest explanation of our finding the two sites to be equivalent is that the dimer results from the homologous association of two identical subunits.

Weak acid-concentration Atot and dissociation constant Ka of plasma proteins in racehorses.

PubMed

Stampfli, H R; Misiaszek, S; Lumsden, J H; Carlson, G P; Heigenhauser, G J

1999-07-01

The plasma proteins are a significant contributor to the total weak acid concentration as a net anionic charge. Due to potential species difference, species-specific values must be confirmed for the weak acid anionic concentrations of proteins (Atot) and the effective dissociation constant for plasma weak acids (Ka). We studied the net anion load Atot of equine plasma protein in 10 clinically healthy mature Standardbred horses. A multi-step titration procedure, using a tonometer covering a titration range of PCO2 from 25 to 145 mmHg at 37 degrees C, was applied on the plasma of these 10 horses. Blood gases (pH, PCO2) and electrolytes required to calculate the strong ion difference ([SID] = [(Na(+) + K(+) + Ca(2+) + Mg(2+))-(Cl(-) + Lac(-) + PO4(2-))]) were simultaneously measured over a physiological pH range from 6.90-7.55. A nonlinear regression iteration to determine Atot and Ka was performed using polygonal regression curve fitting applied to the electrical neutrality equation of the physico-chemical system. The average anion-load Atot for plasma protein of 10 Standardbred horses was 14.89 +/- 0.8 mEq/l plasma and Ka was 2.11 +/- 0.50 x 10(-7) Eq/l (pKa = 6.67). The derived conversion factor (iterated Atot concentration/average plasma protein concentration) for calculation of Atot in plasma is 0.21 mEq/g protein (protein-unit: g/l). This value compares closely with the 0.24 mEq/g protein determined by titration of Van Slyke et al. (1928) and 0.22 mEq/g protein recently published by Constable (1997) for horse plasma. The Ka value compares closely with the value experimentally determined by Constable in 1997 (2.22 x 10(7) Eq/l). Linear regression of a set of experimental data from 5 Thoroughbred horses on a treadmill exercise test, showed excellent correlation with the regression lines not different from identity for the calculated and measured variables pH, HCO3 and SID. Knowledge of Atot and Ka for the horse is useful especially in exercise studies and in

The stoichiometric dissociation constants of carbonic acid in seawater brines from 298 to 267 K

NASA Astrophysics Data System (ADS)

Papadimitriou, Stathys; Loucaides, Socratis; Rérolle, Victoire M. C.; Kennedy, Paul; Achterberg, Eric P.; Dickson, Andrew G.; Mowlem, Matthew; Kennedy, Hilary

2018-01-01

The stoichiometric dissociation constants of carbonic acid (K1C∗ and K2C∗) were determined by measurement of all four measurable parameters of the carbonate system (total alkalinity, total dissolved inorganic carbon, pH on the total proton scale, and CO2 fugacity) in natural seawater and seawater-derived brines, with a major ion composition equivalent to that of Reference Seawater, to practical salinity (SP) 100 and from 25 °C to the freezing point of these solutions and -6 °C temperature minimum. These values, reported in the total proton scale, provide the first such determinations at below-zero temperatures and for SP > 50. The temperature (T, in Kelvin) and SP dependence of the current pK1C∗ and pK2C∗ (as negative common logarithms) within the salinity and temperature ranges of this study (33 ≤ SP ≤ 100, -6 °C ≤ t ≤ 25 °C) is described by the following best-fit equations: pK1C∗ = -176.48 + 6.14528 SP0.5 - 0.127714 SP + 7.396 × 10-5SP2 + (9914.37 - 622.886 SP0.5 + 29.714 SP) T-1 + (26.05129 - 0.666812 SP0.5) lnT (σ = 0.011, n = 62), and pK2C∗ = -323.52692 + 27.557655 SP0.5 + 0.154922 SP - 2.48396 × 10-4 SP2 + (14763.287 - 1014.819 SP0.5 - 14.35223 SP) T-1 + (50.385807 - 4.4630415 SP0.5) lnT (σ = 0.020, n = 62). These functions are suitable for application to investigations of the carbonate system of internal sea ice brines with a conservative major ion composition relative to that of Reference Seawater and within the temperature and salinity ranges of this study.

LUMOS - A Sensitive and Reliable Optode System for Measuring Dissolved Oxygen in the Nanomolar Range

PubMed Central

Lehner, Philipp; Larndorfer, Christoph; Garcia-Robledo, Emilio; Larsen, Morten; Borisov, Sergey M.; Revsbech, Niels-Peter; Glud, Ronnie N.; Canfield, Donald E.; Klimant, Ingo

2015-01-01

Most commercially available optical oxygen sensors target the measuring range of 300 to 2 μmol L-1. However these are not suitable for investigating the nanomolar range which is relevant for many important environmental situations. We therefore developed a miniaturized phase fluorimeter based measurement system called the LUMOS (Luminescence Measuring Oxygen Sensor). It consists of a readout device and specialized “sensing chemistry” that relies on commercially available components. The sensor material is based on palladium(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin embedded in a Hyflon AD 60 polymer matrix and has a KSV of 6.25 x 10-3 ppmv-1. The applicable measurement range is from 1000 nM down to a detection limit of 0.5 nM. A second sensor material based on the platinum(II) analogue of the porphyrin is spectrally compatible with the readout device and has a measurement range of 20 μM down to 10 nM. The LUMOS device is a dedicated system optimized for a high signal to noise ratio, but in principle any phase flourimeter can be adapted to act as a readout device for the highly sensitive and robust sensing chemistry. Vise versa, the LUMOS fluorimeter can be used for read out of less sensitive optical oxygen sensors based on the same or similar indicator dyes, for example for monitoring oxygen at physiological conditions. The presented sensor system exhibits lower noise, higher resolution and higher sensitivity than the electrochemical STOX sensor previously used to measure nanomolar oxygen concentrations. Oxygen contamination in common sample containers has been investigated and microbial or enzymatic oxygen consumption at nanomolar concentrations is presented. PMID:26029920

Mitochondrial benzodiazepine receptor linked to inner membrane ion channels by nanomolar actions of ligands.

PubMed Central

Kinnally, K W; Zorov, D B; Antonenko, Y N; Snyder, S H; McEnery, M W; Tedeschi, H

1993-01-01

The mitochrondrial benzodiazepine receptor (mBzR) binds a subset of benzodiazepines and isoquinoline carboxamides with nanomolar affinity and consists of the voltage-dependent anion channel, the adenine nucleotide translocator, and an 18-kDa protein. The effect of ligands of the mBzR on two inner mitochondrial membrane channel activities was determined with patch-clamp techniques. The relative inhibitory potencies of the drugs resemble their binding affinities for the mBzR. Ro5-4864 and protoporphyrin IX inhibit activity of the multiple conductance channel (MCC) and the mitochondrial centum-picosiemen (mCtS) channel activities at nanomolar concentrations. PK11195 inhibits mCtS activity at similar levels. Higher concentrations of protoporphyrin IX induce MCC but possibly not mCtS activity. Clonazepam, which has low affinity for mBzR, is at least 500 times less potent at both channel activities. Ro15-1788, which also has a low mBzR affinity, inhibits MCC at very high concentrations (16 microM). The findings indicate an association of these two channel activities with the proteins forming the mBzR complex and are consistent with an interaction of inner and outer membrane channels. PMID:7679505

Dissociative recombination of N2/+/ in the ionosphere

NASA Technical Reports Server (NTRS)

Torr, M. R.; Torr, D. G.

1979-01-01

N2(+) ion measurements are examined which were made with the Atmospheric Explorer-C satellite during a phase of solar activity in 1978 that was significantly higher than near the earlier minimum. It is found that the major source of N2(+) is photoionization, rather than charge exchange with O(+) (2D), and that the major loss process above 300 km is dissociative recombination with electrons. A data sample for which the electron temperature (T sub e) covered the range from 1000 to 3400 K is used to evaluate the rate constant, alpha, for the dissociative-recombination process. The results show good agreement with laboratory measurements given by the expression: alpha = 1.8 x 10 to the -7th (T sub e/300) to the -0.39th cu cm/sec.

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…

Dissociative absorption: An empirically unique, clinically relevant, dissociative factor.

PubMed

Soffer-Dudek, Nirit; Lassri, Dana; Soffer-Dudek, Nir; Shahar, Golan

2015-11-01

Research of dissociative absorption has raised two questions: (a) Is absorption a unique dissociative factor within a three-factor structure, or a part of one general dissociative factor? Even when three factors are found, the specificity of the absorption factor is questionable. (b) Is absorption implicated in psychopathology? Although commonly viewed as "non-clinical" dissociation, absorption was recently hypothesized to be specifically associated with obsessive-compulsive symptoms. To address these questions, we conducted exploratory and confirmatory factor analyses on 679 undergraduates. Analyses supported the three-factor model, and a "purified" absorption scale was extracted from the original inclusive absorption factor. The purified scale predicted several psychopathology scales. As hypothesized, absorption was a stronger predictor of obsessive-compulsive symptoms than of general psychopathology. In addition, absorption was the only dissociative scale that longitudinally predicted obsessive-compulsive symptoms. We conclude that absorption is a unique and clinically relevant dissociative tendency that is particularly meaningful to obsessive-compulsive symptoms. Copyright © 2015 Elsevier Inc. All rights reserved.

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. Copyright © 2012 Elsevier Inc. All rights reserved.

Dissociation and serenity induction.

PubMed

Zoellner, Lori A; Sacks, Matthew B; Foa, Edna B

2007-09-01

Dissociation is a common experience during or immediately after a traumatic event; yet, most of the current knowledge regarding dissociation is retrospective in nature. The aim of the present study investigated a non-pharmacological method of dissociative induction with a clinical sample. Participants with PTSD and non-trauma exposed participants were randomly assigned to receive either a dissociative induction, or a serenity induction, based on modified Velten mood induction procedures. Participants receiving the dissociative induction reported higher state-dissociation than those receiving the serenity induction. The PTSD group reported greater state dissociation than the non-trauma exposed group, regardless of induction. State dissociation was related to trait dissociation, PTSD severity, and depression. The present results provide an initial demonstration of the viability for inducing state dissociation in the laboratory with a PTSD sample.

Tracking scientific interest in the dissociative disorders: a study of scientific publication output 1984-2003.

PubMed

Pope, Harrison G; Barry, Steven; Bodkin, Alexander; Hudson, James I

2006-01-01

We attempted to track scientific interest in dissociative amnesia and dissociative identity disorder by estimating the annual output of publications regarding these entities over the last 20 years. Using a standard medical index, PsycINFO, we counted the number of indexed publications involving dissociative amnesia and dissociative identity disorder listed for each year. We then compared these rates with those of well-established diagnoses such as anorexia nervosa, alcohol abuse, and schizophrenia. We also systematically reviewed all publications involving dissociative amnesia that appeared in 2003. Annual publications involving dissociative amnesia and dissociative identity disorder rose from low levels in the 1980's to a sharp peak in the mid 1990's, followed by an equally sharp decline to only about one quarter of their peak levels by 2002 and 2003. In contrast, all of the 25 comparison diagnoses in our survey showed constant or steadily rising publication rates; none showed the 'bubble' pattern of the dissociative disorders. Of the 34 papers involving dissociative amnesia identified by PsycINFO for 2003, 10 (32%) appeared skeptical of the validity of dissociative amnesia and/or recovered-memory therapy. Despite a detailed search using multiple medical indices and search terms, we could find only 13 explicit cases of individuals with dissociative amnesia worldwide in the 2003 literature. Dissociative amnesia and dissociative identity disorder have not generated consistent scientific interest over the years, but instead apparently enjoyed a brief period of fashion that now has waned. Overall, our observations suggest that these diagnostic entities presently do not command widespread scientific acceptance. Copyright 2006 S. Karger AG, Basel.

Modeling electrostatic and heterogeneity effects on proton dissociation from humic substances

USGS Publications Warehouse

Tipping, E.; Reddy, M.M.; Hurley, M.A.

1990-01-01

The apparent acid dissociation constant of humic substances increases by 2-4 pK units as ionization of the humic carboxylate groups proceeds. This change in apparent acid strength is due in part to the increase in electrical charge on the humic molecules as protons are shed. In addition, proton dissociation reactions are complicated because humic substances are heterogeneous with respect to proton dissociating groups and molecular size. In this paper, we use the Debye-Hu??ckel theory to describe the effects of electrostatic interactions on proton dissociation of humic substances. Simulations show that, for a size-heterogeneous system of molecules, the weight-average molecular weight is preferable to the number-average value for averaging the effects of electrostatic interactions. Analysis of published data on the proton dissociation of fulvic acid from the Suwannee River shows that the electrostatic interactions can be satisfactorily described by a hypothetical homogeneous compound having a molecular weight of 1000 (similar to the experimentally determined weight-average value). Titration data at three ionic strengths, for several fulvic acid concentrations, and in the pH range from 2.9 to 6.4 can be fitted with three adjustable parameters (pK??int values), given information on molecular size and carboxylate group content. ?? 1990 American Chemical Society.

Dissociation in patients with dissociative seizures: relationships with trauma and seizure symptoms.

PubMed

Pick, S; Mellers, J D C; Goldstein, L H

2017-05-01

This study aimed to extend the current understanding of dissociative symptoms experienced by patients with dissociative (psychogenic, non-epileptic) seizures (DS), including psychological and somatoform types of symptomatology. An additional aim was to assess possible relationships between dissociation, traumatic experiences, post-traumatic symptoms and seizure manifestations in this group. A total of 40 patients with DS were compared with a healthy control group (n = 43), matched on relevant demographic characteristics. Participants completed several self-report questionnaires, including the Multiscale Dissociation Inventory (MDI), Somatoform Dissociation Questionnaire-20, Traumatic Experiences Checklist and the Post-Traumatic Diagnostic Scale. Measures of seizure symptoms and current emotional distress (Hospital Anxiety and Depression Scale) were also administered. The clinical group reported significantly more psychological and somatoform dissociative symptoms, trauma, perceived impact of trauma, and post-traumatic symptoms than controls. Some dissociative symptoms (i.e. MDI disengagement, MDI depersonalization, MDI derealization, MDI memory disturbance, and somatoform dissociation scores) were elevated even after controlling for emotional distress; MDI depersonalization scores correlated positively with trauma scores while seizure symptoms correlated with MDI depersonalization, derealization and identity dissociation scores. Exploratory analyses indicated that somatoform dissociation specifically mediated the relationship between reported sexual abuse and DS diagnosis, along with depressive symptoms. A range of psychological and somatoform dissociative symptoms, traumatic experiences and post-traumatic symptoms are elevated in patients with DS relative to healthy controls, and seem related to seizure manifestations. Further studies are needed to explore peri-ictal dissociative experiences in more detail.

Evidence that Ribulose 1,5-Bisphosphate (RuBP) Binds to Inactive Sites of RuBP Carboxylase in Vivo and an Estimate of the Rate Constant for Dissociation 1

PubMed Central

Cardon, Zoe G.; Mott, Keith A.

1989-01-01

The binding of ribulose 1,5-bisphosphate (RuBP) to inactive (noncarbamylated) sites of the enzyme RuBP carboxylase in vivo was investigated in Spinacia oleracea and Helianthus annuus. The concentrations of RuBP and inactive sites were determined in leaf tissue as a function of time after a change to darkness. RuBP concentrations fell rapidly after the change to darkness and were approximately equal to the concentration of inactive sites after 60 s. Variations in the concentration of inactive sites, which were induced by differences in the light intensity before the light-dark transition, correlated with the concentration of RuBP between 60 and 120 s after the change to darkness. These data are discussed as evidence that RuBP binds to inactive sites of RuBP carboxylase in vivo. After the concentration of RuBP fell below that of inactive sites (at times longer than 60 s of darkness), the decline in RuBP was logarithmic with time. This would be expected if the dissociation of RuBP from inactive sites controlled the decline in RuBP concentration. These data were used to estimate the rate constant for dissociation of RuBP from inactive sites in vivo. PMID:16666692

Activation of Peptide ions by blackbody radiation: factors that lead to dissociation kinetics in the rapid energy exchange limit.

PubMed

Price, W D; Williams, E R

1997-11-20

Unimolecular rate constants for blackbody infrared radiative dissociation (BIRD) were calculated for the model protonated peptide (AlaGly)(n) (n = 2-32) using a variety of dissociation parameters. Combinations of dissociation threshold energies ranging from 0.8 to 1.7 eV and transition entropies corresponding to Arrhenius preexponential factors ranging from very "tight" (A(infinity) = 10(9.9) s(-1)) to "loose" (A(infinity) = 10(16.8) s(-1)) were selected to represent dissociation parameters within the experimental temperature range (300-520 K) and kinetic window (k(uni) = 0.001-0.20 s(-1)) typically used in the BIRD experiment. Arrhenius parameters were determined from the temperature dependence of these values and compared to those in the rapid energy exchange (REX) limit. In this limit, the internal energy of a population of ions is given by a Boltzmann distribution, and kinetics are the same as those in the traditional high-pressure limit. For a dissociation process to be in this limit, the rate of photon exchange between an ion and the vacuum chamber walls must be significantly greater than the dissociation rate. Kinetics rapidly approach the REX limit either as the molecular size or threshold dissociation energy increases or as the transition-state entropy or experimental temperature decreases. Under typical experimental conditions, peptide ions larger than 1.6 kDa should be in the REX limit. Smaller ions may also be in the REX limit depending on the value of the threshold dissociation energy and transition-state entropy. Either modeling or information about the dissociation mechanism must be known in order to confirm REX limit kinetics for these smaller ions. Three principal factors that lead to the size dependence of REX limit kinetics are identified. With increasing molecular size, rates of radiative absorption and emission increase, internal energy distributions become relatively narrower, and the microcanonical dissociation rate constants increase more

Activation of Peptide Ions by Blackbody Radiation: Factors That Lead to Dissociation Kinetics in the Rapid Energy Exchange Limit

PubMed Central

Price, William D.

2005-01-01

Unimolecular rate constants for blackbody infrared radiative dissociation (BIRD) were calculated for the model protonated peptide (AlaGly)n (n = 2–32) using a variety of dissociation parameters. Combinations of dissociation threshold energies ranging from 0.8 to 1.7 eV and transition entropies corresponding to Arrhenius preexponential factors ranging from very “tight” (A∞ = 109.9 s−1) to “loose” (A∞ = 1016.8 s−1) were selected to represent dissociation parameters within the experimental temperature range (300–520 K) and kinetic window (kuni = 0.001–0.20 s−1) typically used in the BIRD experiment. Arrhenius parameters were determined from the temperature dependence of these values and compared to those in the rapid energy exchange (REX) limit. In this limit, the internal energy of a population of ions is given by a Boltzmann distribution, and kinetics are the same as those in the traditional high-pressure limit. For a dissociation process to be in this limit, the rate of photon exchange between an ion and the vacuum chamber walls must be significantly greater than the dissociation rate. Kinetics rapidly approach the REX limit either as the molecular size or threshold dissociation energy increases or as the transition-state entropy or experimental temperature decreases. Under typical experimental conditions, peptide ions larger than 1.6 kDa should be in the REX limit. Smaller ions may also be in the REX limit depending on the value of the threshold dissociation energy and transition-state entropy. Either modeling or information about the dissociation mechanism must be known in order to confirm REX limit kinetics for these smaller ions. Three principal factors that lead to the size dependence of REX limit kinetics are identified. With increasing molecular size, rates of radiative absorption and emission increase, internal energy distributions become relatively narrower, and the microcanonical dissociation rate constants increase more slowly

Dissociation Energetics and Mechanisms of Leucine Enkephalin (M + H)+ and (2M + X)+ Ions (X = H, Li, Na, K, and Rb) Measured by Blackbody Infrared Radiative Dissociation

PubMed Central

Schnier, Paul D.; Price, William D.; Strittmatter, Eric F.; Williams, Evan R.

2005-01-01

The dissociation kinetics of protonated leucine enkephalin and its proton and alkali metal bound dimers were investigated by blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Protonated leucine enkephalin dissociates to form b4 and (M−H2O)+ ions with an average activation energy (Ea) of 1.1 eV and an A factor of 1010.5 s−1. The value of the A factor indicates that these dissociation processes are rearrangements. The b4 ions subsequently dissociate to form a4 ions via a process with a relatively high activation energy (1.3 eV), but one that is entropically favored. For the cationized dimers, the thermal stability decreases with increasing cation size, consistent with a simple electrostatic interaction in these noncovalent ion–molecule complexes. The Ea and A factors are indistinguishable within experimental error with values of ~1.5 eV and 1017 s−1, respectively. Although not conclusive, results from master equation modeling indicate that all these BIRD processes, except for b4 → a4, are in the rapid energy exchange limit. In this limit, the internal energy of the precursor ion population is given by a Boltzmann distribution and information about the energetics and dynamics of the reaction are obtained directly from the measured Arrhenius parameters. PMID:16554908

Dissociation energetics and mechanisms of leucine enkephalin (M + H)+ and (2M + X)+ ions (X = H, Li, Na, K, and Rb) measured by blackbody infrared radiative dissociation.

PubMed

Schnier, P D; Price, W D; Strittmatter, E F; Williams, E R

1997-08-01

The dissociation kinetics of protonated leucine enkephalin and its proton and alkali metal bound dimers were investigated by blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Protonated leucine enkephalin dissociates to form b(4) and (M-H(2)O)(+) ions with an average activation energy (E(a)) of 1.1 eV and an A factor of 10(10.5) s(-1). The value of the A factor indicates that these dissociation processes are rearrangements. The b(4) ions subsequently dissociate to form a(4) ions via a process with a relatively high activation energy (1.3 eV), but one that is entropically favored. For the cationized dimers, the thermal stability decreases with increasing cation size, consistent with a simple electrostatic interaction in these noncovalent ion-molecule complexes. The E(a) and A factors are indistinguishable within experimental error with values of approximately 1.5 eV and 10(17) s(-1), respectively. Although not conclusive, results from master equation modeling indicate that all these BIRD processes, except for b(4) --> a(4), are in the rapid energy exchange limit. In this limit, the internal energy of the precursor ion population is given by a Boltzmann distribution and information about the energetics and dynamics of the reaction are obtained directly from the measured Arrhenius parameters.

Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

NASA Astrophysics Data System (ADS)

Ma, Shu-Cui; Wang, Zhi-Gang; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

2015-02-01

The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation-deprotonation behavior was determined by continuous acid-base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m2/g and large numbers of surface hydroxyl functional groups (i.e. tbnd Si-OH, tbnd Fe-OH, and tbnd Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K1, log K2) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation-deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent.

Determination of stability constants of aminoglycoside antibiotics with their metal complexes

NASA Astrophysics Data System (ADS)

Tiwow, Vanny M. A.

2014-03-01

One group of aminoglycoside antibiotics contains aminosugars. The aminosugar neomycin B with its derivate product neamine (2-Deoxy-4-0-(2,6-diamino-2,6-dideoxy-α-D-glucopyranosyl)-D-Streptamine) was identified as a free ligands and metal complexes. In particular, the stability constants of metal complexes by potentiometric titration techniques were investigated. Our previous study had determined the acid dissociation constants of these aminosugars with few metal complexes in fair depth. In this work, the complexation of two pyridine-containing amino alcohols and an amino sugar (neamine) have been measured potentiometrically. For instance, the stability constant of copper(II) complexation were determine and the model system generated an excellent fit. Stability constants with several metals have been determined and will be reported.

Direct dynamics simulations of the unimolecular dissociation of dioxetane: Probing the non-RRKM dynamics

NASA Astrophysics Data System (ADS)

Malpathak, Shreyas; Ma, Xinyou; Hase, William L.

2018-04-01

In a previous UB3LYP/6-31G* direct dynamics simulation, non-Rice-Ramsperger-Kassel-Marcus (RRKM) unimolecular dynamics was found for vibrationally excited 1,2-dioxetane (DO); [R. Sun et al., J. Chem. Phys. 137, 044305 (2012)]. In the work reported here, these dynamics are studied in more detail using the same direct dynamics method. Vibrational modes of DO were divided into 4 groups, based on their characteristic motions, and each group excited with the same energy. To compare with the dynamics of these groups, an additional group of trajectories comprising a microcanonical ensemble was also simulated. The results of these simulations are consistent with the previous study. The dissociation probability, N(t)/N(0), for these excitation groups were all different. Groups A, B, and C, without initial excitation in the O-O stretch reaction coordinate, had a time lag to of 0.25-1.0 ps for the first dissociation to occur. Somewhat surprisingly, the C-H stretch Group A and out-of-plane motion Group C excitations had exponential dissociation probabilities after to, with a rate constant ˜2 times smaller than the anharmonic RRKM value. Groups B and D, with excitation of the H-C-H bend and wag, and ring bend and stretch modes, respectively, had bi-exponential dissociation probabilities. For Group D, with excitation localized in the reaction coordinate, the initial rate constant is ˜7 times larger than the anharmonic RRKM value, substantial apparent non-RRKM dynamics. N(t)/N(0) for the random excitation trajectories was non-exponential, indicating intrinsic non-RRKM dynamics. For the trajectory integration time of 13.5 ps, 9% of these trajectories did not dissociate in comparison to the RRKM prediction of 0.3%. Classical power spectra for these trajectories indicate they have regular intramolecular dynamics. The N(t)/N(0) for the excitation groups are well described by a two-state coupled phase space model. From the intercept of N(t)/N(0) with random excitation, the

Contemporary concepts of dissociation.

PubMed

Avdibegović, Esmina

2012-10-01

The concept of dissociation was developed in the late 19th century by Pierre Janet for conditions of "double consciousness" in hypnosis, hysteria, spirit possession and mediumship. He defined dissociation as a deficit in the capacity of integration of two or more different "systems of ideas and functions that constitute personality", and suggested that it can be related to a genetic component, to severe illness and fatigue, and particularly to experiencing adverse, potentially traumatizing events. By the late 20th century, various and often contradictory concepts of dissociation were suggested, which were either insufficient or exceedingly including when compared to the original idea. Currently, dissociation is used to describe a wide range of normal and abnormal phenomena as a process in which behaviour, thoughts and emotions can become separated one from another. A complete presentation of mechanisms involved in dissociation is still unknown. Scientific research on basic processes of dissociation is derived mainly from studies of hypnosis and post-traumatic stress disorder. Given the controversies in modern concepts of dissociation, some researchers and theorists suggest return to the original understanding of dissociation as a basic premise for the further development of the concept of dissociation.

Calculation of rates of exciton dissociation into hot charge-transfer states in model organic photovoltaic interfaces

NASA Astrophysics Data System (ADS)

Vázquez, Héctor; Troisi, Alessandro

2013-11-01

We investigate the process of exciton dissociation in ordered and disordered model donor/acceptor systems and describe a method to calculate exciton dissociation rates. We consider a one-dimensional system with Frenkel states in the donor material and states where charge transfer has taken place between donor and acceptor. We introduce a Green's function approach to calculate the generation rates of charge-transfer states. For disorder in the Frenkel states we find a clear exponential dependence of charge dissociation rates with exciton-interface distance, with a distance decay constant β that increases linearly with the amount of disorder. Disorder in the parameters that describe (final) charge-transfer states has little effect on the rates. Exciton dissociation invariably leads to partially separated charges. In all cases final states are “hot” charge-transfer states, with electron and hole located far from the interface.

ab initio calculation of the rate of vibrational relaxation and thermal dissociation of hydrogen by helium at high temperatures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dove, J.E.; Raynor, S.

The master equation for the thermal dissociation of para-H/sub 2/ infinitely dilute in He, was solved for temperatures of 1000 to 10,000/sup 0/K. Transition probabilities, used in the master equation, were obtained, in the case of energy transfer transitions, from distorted wave and quasi-classical trajectory calculations and, for dissociative processes, from trajectory calculations alone. An ab initio potential was used. From the solution, values of the dissociation rate constant, vibrational relaxation times, and incubation times for dissociation and vibrational relaxation were calculated. The sensitivity of the calculated results to variations in the transition probabilities was examined. Vibrational relaxation is mostmore » sensitive to simultaneous transitions in vibration and rotation (VRT processes); pure rotational (RT) transitions also have a substantial effect. Dissociation is most strongly affected by RT processes, but changes in VRT and groups of dissociative transitions also have a significant effect. However complete suppression of all dissociative transitions except those from levels immediately next to the continuum lowers the dissociation rates only by a factor of about 2. The location of the dissociation ''bottleneck'' is discussed. 5 figures, 3 tables.« less

The co-occurrence of PTSD and dissociation: differentiating severe PTSD from dissociative-PTSD.

PubMed

Armour, Cherie; Karstoft, Karen-Inge; Richardson, J Don

2014-08-01

A dissociative-posttraumatic stress disorder (PTSD) subtype has been included in the DSM-5. However, it is not yet clear whether certain socio-demographic characteristics or psychological/clinical constructs such as comorbid psychopathology differentiate between severe PTSD and dissociative-PTSD. The current study investigated the existence of a dissociative-PTSD subtype and explored whether a number of trauma and clinical covariates could differentiate between severe PTSD alone and dissociative-PTSD. The current study utilized a sample of 432 treatment seeking Canadian military veterans. Participants were assessed with the Clinician Administered PTSD Scale (CAPS) and self-report measures of traumatic life events, depression, and anxiety. CAPS severity scores were created reflecting the sum of the frequency and intensity items from each of the 17 PTSD and 3 dissociation items. The CAPS severity scores were used as indicators in a latent profile analysis (LPA) to investigate the existence of a dissociative-PTSD subtype. Subsequently, several covariates were added to the model to explore differences between severe PTSD alone and dissociative-PTSD. The LPA identified five classes: one of which constituted a severe PTSD group (30.5 %), and one of which constituted a dissociative-PTSD group (13.7 %). None of the included, demographic, trauma, or clinical covariates were significantly predictive of membership in the dissociative-PTSD group compared to the severe PTSD group. In conclusion, a significant proportion of individuals report high levels of dissociation alongside their PTSD, which constitutes a dissociative-PTSD subtype. Further investigation is needed to identify which factors may increase or decrease the likelihood of membership in a dissociative-PTSD subtype group compared to a severe PTSD only group.

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.

Dissociation in Psychiatric Disorders: A Meta-Analysis of Studies Using the Dissociative Experiences Scale.

PubMed

Lyssenko, Lisa; Schmahl, Christian; Bockhacker, Laura; Vonderlin, Ruben; Bohus, Martin; Kleindienst, Nikolaus

2018-01-01

Dissociation is a complex, ubiquitous construct in psychopathology. Symptoms of dissociation are present in a variety of mental disorders and have been connected to higher burden of illness and poorer treatment response, and not only in disorders with high levels of dissociation. This meta-analysis offers a systematic and evidence-based study of the prevalence and distribution of dissociation, as assessed by the Dissociative Experiences Scale, within different categories of mental disorders, and it updates an earlier meta-analysis. More than 1,900 original publications were screened, and 216 were included in the meta-analysis, comprising 15,219 individuals in 19 diagnostic categories. The largest mean dissociation scores were found in dissociative disorders (mean scores >35), followed by posttraumatic stress disorder, borderline personality disorder, and conversion disorder (mean scores >25). Somatic symptom disorder, substance-related and addictive disorders, feeding and eating disorders, schizophrenia, anxiety disorder, OCD, and most affective disorders also showed mean dissociation scores >15. Bipolar disorders yielded the lowest dissociation scores (mean score, 14.8). The findings underline the importance of careful psychopathological assessment of dissociative symptoms in the entire range of mental disorders.

A Dispersion-Dominated Chromogenic Strategy for Colorimetric Sensing of Glutathione at the Nanomolar Level Using Gold Nanoparticles.

PubMed

Xianyu, Yunlei; Xie, Yangzhouyun; Wang, Nuoxin; Wang, Zhuo; Jiang, Xingyu

2015-11-04

A dispersion-dominated chromogenic strategy for glutathione sensing is developed. Glutathione prevents the aggregation of arginine-modified gold nanoparticles via mercury-thiol interaction, which allows for glutathione sensing at the nanomolar level (10.9 × 10(-9) m) with facile operation and naked-eye readout. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissociative disorders in medical settings.

PubMed

MacPhee, Edward

2013-10-01

Despite the challenges of conducting research on dissociation and the dissociative disorders, our understanding has grown greatly over the past three decades, including our knowledge of the often overlooked sensorimotor manifestations of dissociation, more commonly referred to as somatoform dissociation. This article will first review the definitions and presentations of dissociation in general along with recent research on the concept of somatoform dissociation. Then, each of the dissociative disorders and conversion disorder will be discussed in further detail as well as how they might present in a medical setting. Current recommendations for diagnosis and treatment will also be provided.

An amorphous silicon photodiode microfluidic chip to detect nanomolar quantities of HIV-1 virion infectivity factor.

PubMed

Vistas, Cláudia R; Soares, Sandra S; Rodrigues, Rogério M M; Chu, Virginia; Conde, João P; Ferreira, Guilherme N M

2014-08-07

A hydrogenated amorphous silicon (a-Si:H) photosensor was explored for the quantitative detection of a HIV-1 virion infectivity factor (Vif) at a detection limit in the single nanomolar range. The a-Si:H photosensor was coupled with a microfluidic channel that was functionalized with a recombinant single chain variable fragment antibody. The biosensor selectively recognizes HIV-1 Vif from human cell extracts.

Prediction of Rate Constant for Supramolecular Systems with Multiconfigurations.

PubMed

Guo, Tao; Li, Haiyan; Wu, Li; Guo, Zhen; Yin, Xianzhen; Wang, Caifen; Sun, Lixin; Shao, Qun; Gu, Jingkai; York, Peter; Zhang, Jiwen

2016-02-25

The control of supramolecular systems requires a thorough understanding of their dynamics, especially on a molecular level. It is extremely difficult to determine the thermokinetic parameters of supramolecular systems, such as drug-cyclodextrin complexes with fast association/dissociation processes by experimental techniques. In this paper, molecular modeling combined with novel mathematical relationships integrating the thermodynamic/thermokinetic parameters of a series of isomeric multiconfigurations to predict the overall parameters in a range of pH values have been employed to study supramolecular dynamics at the molecular level. A suitable form of Eyring's equation was derived and a two-stage model was introduced. The new approach enabled accurate prediction of the apparent dissociation/association (k(off)/k(on)) and unbinding/binding (k-r/kr) rate constants of the ubiquitous multiconfiguration complexes of the supramolecular system. The pyronine Y (PY) was used as a model system for the validation of the presented method. Interestingly, the predicted k(off) value ((40 ± 1) × 10(5) s(-1), 298 K) of PY is largely in agreement with that previously determined by fluorescence correlation spectroscopy ((5 ± 3) × 10(5) s(-1), 298 K). Moreover, the k(off)/k(on) and k-r/kr for flurbiprofen-β-cylcodextrin and ibuprofen-β-cyclodextrin systems were also predicted and suggested that the association processes are diffusion-controlled. The methodology is considered to be especially useful in the design and selection of excipients for a supramolecular system with preferred association and dissociation rate constants and understanding their mechanisms. It is believed that this new approach could be applicable to a wide range of ligand-receptor supramolecular systems and will surely help in understanding their complex mechanism.

Effect of pressure on the dissociation constant of boric acid in water and seawater

NASA Astrophysics Data System (ADS)

Millero, Frank J.; Ward, Gary K.; Surdo, Antonio Lo; Huang, Fen

2012-01-01

The sound speeds of boric acid and sodium borate in water and 0.725 m NaCl have been measured from 0 to 50 °C and to near 1 molal. These results have been used to determine the partial molal adiabatic compressibilities of B(OH) 3 and NaB(OH) 4. The partial molal volumes, v¯(i), and compressibilities, κ¯(i), have been used to estimate the changes in the volume (Δ V) and compressibility (Δ κ) for the dissociation of boric acid in water and average seawater (0.725 m NaCl, SA ˜ 35 g/kg) B(OH)3+H2O=H++B(OH)4- where

Nanomolar Trace Metal Analysis of Copper at Gold Microband Arrays

NASA Astrophysics Data System (ADS)

Wahl, A.; Dawson, K.; Sassiat, N.; Quinn, A. J.; O'Riordan, A.

2011-08-01

This paper describes the fabrication and electrochemical characterization of gold microband electrode arrays designated as a highly sensitive sensor for trace metal detection of copper in drinking water samples. Gold microband electrodes have been routinely fabricated by standard photolithographic methods. Electrochemical characterization were conducted in 0.1 M H2SO4 and found to display characteristic gold oxide formation and reduction peaks. The advantages of gold microband electrodes as trace metal sensors over currently used methods have been investigated by employing under potential deposition anodic stripping voltammetry (UPD-ASV) in Cu2+ nanomolar concentrations. Linear correlations were observed for increasing Cu2+ concentrations from which the concentration of an unknown sample of drinking water was estimated. The results obtained for the estimation of the unknown trace copper concentration in drinking was in good agreement with expected values.

Multiple exciton dissociation in CdSe quantum dots by ultrafast electron transfer to adsorbed methylene blue.

PubMed

Huang, Jier; Huang, Zhuangqun; Yang, Ye; Zhu, Haiming; Lian, Tianquan

2010-04-07

Multiexciton generation in quantum dots (QDs) may provide a new approach for improving the solar-to-electric power conversion efficiency in QD-based solar cells. However, it remains unclear how to extract these excitons before the ultrafast exciton-exciton annihilation process. In this study we investigate multiexciton dissociation dynamics in CdSe QDs adsorbed with methylene blue (MB(+)) molecules by transient absorption spectroscopy. We show that excitons in QDs dissociate by ultrafast electron transfer to MB(+) with an average time constant of approximately 2 ps. The charge separated state is long-lived (>1 ns), and the charge recombination rate increases with the number of dissociated excitons. Up to three MB(+) molecules per QD can be reduced by exciton dissociation. Our result demonstrates that ultrafast interfacial charge separation can effectively compete with exciton-exciton annihilation, providing a viable approach for utilizing short-lived multiple excitons in QDs.

Prochlorococcus can use the Pro1404 transporter to take up glucose at nanomolar concentrations in the Atlantic Ocean

PubMed Central

Muñoz-Marín, María del Carmen; Luque, Ignacio; Zubkov, Mikhail V.; Hill, Polly G.; Diez, Jesús; García-Fernández, José Manuel

2013-01-01

Prochlorococcus is responsible for a significant part of CO2 fixation in the ocean. Although it was long considered an autotrophic cyanobacterium, the uptake of organic compounds has been reported, assuming they were sources of limited biogenic elements. We have shown in laboratory experiments that Prochlorococcus can take up glucose. However, the mechanisms of glucose uptake and its occurrence in the ocean have not been shown. Here, we report that the gene Pro1404 confers capability for glucose uptake in Prochlorococcus marinus SS120. We used a cyanobacterium unable to take up glucose to engineer strains that express the Pro1404 gene. These recombinant strains were capable of specific glucose uptake over a wide range of glucose concentrations, showing multiphasic transport kinetics. The Ks constant of the high affinity phase was in the nanomolar range, consistent with the average concentration of glucose in the ocean. Furthermore, we were able to observe glucose uptake by Prochlorococcus in the central Atlantic Ocean, where glucose concentrations were 0.5–2.7 nM. Our results suggest that Prochlorococcus are primary producers capable of tuning their metabolism to energetically benefit from environmental conditions, taking up not only organic compounds with key limiting elements in the ocean, but also molecules devoid of such elements, like glucose. PMID:23569224

Dissociative disorders in DSM-5.

PubMed

Spiegel, David; Loewenstein, Richard J; Lewis-Fernández, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardeña, Etzel; Brown, Richard J; Dell, Paul F

2011-12-21

We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining diagnostic criteria. This paper reviews clinical, phenomenological, epidemiological, cultural, and neurobiological data related to the DDs in order to generate an up-to-date, evidence-based set of DD diagnoses and diagnostic criteria for DSM-5. First, we review the definitions of dissociation and the differences between the definitions of dissociation and conceptualization of DDs in the DSM-IV-TR and the ICD-10, respectively. Also, we review more general conceptual issues in defining dissociation and dissociative disorders. Based on this review, we propose a revised definition of dissociation for DSM-5 and discuss the implications of this definition for understanding dissociative symptoms and disorders. We make the following recommendations for DSM-5: 1. Depersonalization Disorder (DPD) should include derealization symptoms as well. 2. Dissociative Fugue should become a subtype of Dissociative Amnesia (DA). 3. The diagnostic criteria for DID should be changed to emphasize the disruptive nature of the dissociation and amnesia for everyday as well as traumatic events. The experience of possession should be included in the definition of identity disruption. 4. Dissociative Trance Disorder should be included in the Unspecified Dissociative Disorder (UDD) category. There is a growing body of evidence linking the dissociative disorders to a trauma history, and to specific neural mechanisms. © 2011 Wiley Periodicals, Inc.

Dissociative disorders in DSM-5.

PubMed

Spiegel, David; Loewenstein, Richard J; Lewis-Fernández, Roberto; Sar, Vedat; Simeon, Daphne; Vermetten, Eric; Cardeña, Etzel; Dell, Paul F

2011-09-01

We present recommendations for revision of the diagnostic criteria for the Dissociative Disorders (DDs) for DSM-5. The periodic revision of the DSM provides an opportunity to revisit the assumptions underlying specific diagnoses and the empirical support, or lack of it, for the defining diagnostic criteria. This paper reviews clinical, phenomenological, epidemiological, cultural, and neurobiological data related to the DDs in order to generate an up-to-date, evidence-based set of DD diagnoses and diagnostic criteria for DSM-5. First, we review the definitions of dissociation and the differences between the definitions of dissociation and conceptualization of DDs in the DSM-IV-TR and the ICD-10, respectively. Also, we review more general conceptual issues in defining dissociation and dissociative disorders. Based on this review, we propose a revised definition of dissociation for DSM-5 and discuss the implications of this definition for understanding dissociative symptoms and disorders. We make the following recommendations for DSM-5: 1. Depersonalization Disorder (DPD) should derealization symptoms as well. 2. Dissociative Fugue should become a subtype of Dissociative Amnesia (DA). 3. The diagnostic criteria for DID should be changed to emphasize the disruptive nature of the dissociation and amnesia for everyday as well as traumatic events. The experience of possession should be included in the definition of identity disruption. 4. Should Dissociative Trance Disorder should be included in the Unspecified Dissociative Disorder (UDD) category. There is a growing body of evidence linking the dissociative disorders to a trauma history, and to specific neural mechanisms. © 2011 Wiley-Liss, Inc.

Predictors of trait dissociation and peritraumatic dissociation induced via cold pressor.

PubMed

Gómez-Pérez, Lydia; López-Martínez, Alicia Eva; Asmundson, Gordon John Glenn

2013-11-30

Understanding which factors predict individual dissociative response during stressful situations is important to clarify the nature of dissociation and the mechanisms associated to its use as a coping strategy. The present study examined (1) whether experiential avoidance (EA), anxiety sensitivity (AS), depressive symptoms, and state anxiety concurrently predicted trait dissociation (TD)-absorption, amnesia, depersonalization, and total TD scores-and laboratory induced dissociation (LID); and (2) whether TD and catastrophizing predicted LID. We also examined whether catastrophizing mediated the relationships between both AS and depressive symptoms and LID. A total of 101 female undergraduate students participated in a cold pressor task, which significantly induced dissociation. Results of hierarchical regression analyses showed that AS at Time 1 (9 months before the experimental session), as well as depressive symptoms and catastrophizing at the time of the experiment (Time 2), predicted LID at Time 2. Depressive symptoms at Time 2 predicted total TD, absorption, and amnesia scores. AS at Time 1 and depressive symptoms at Time 2 predicted depersonalization. AS, depressive symptoms, and catastrophizing seem to facilitate the use of dissociative strategies by healthy individuals, even in response to non-traumatic but discomforting stress. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

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.

Development of Amidine-Based Sphingosine Kinase 1 Nanomolar Inhibitors and Reduction of Sphingosine 1-Phosphate in Human Leukemia Cells

PubMed Central

Kennedy, Andrew J.; Mathews, Thomas P.; Kharel, Yugesh; Field, Saundra D.; Moyer, Morgan L.; East, James E.; Houck, Joseph D.; Lynch, Kevin R.; Macdonald, Timothy L.

2011-01-01

Sphingosine 1-phosphate (S1P) is a bioactive lipid that has been identified as an accelerant of cancer progression. The sphingosine kinases (SphKs) are the sole producers of S1P and thus SphK inhibitors may prove effective in cancer mitigation and chemosensitization. Of the two SphKs, SphK1 overexpression has been observed in a myriad of cancer cell lines and tissues, and has been recognized as the presumptive target over that of the poorly characterized SphK2. Herein, we present the design and synthesis of amidine-based nanomolar SphK1 subtype-selective inhibitors. A homology model of SphK1, trained with this library of amidine inhibitors, was then used to predict the activity of additional, more potent, inhibitors. Lastly, select amidine inhibitors were validated in human leukemia U937 cells, where they significantly reduced endogenous S1P levels at nanomolar concentrations. PMID:21495716

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.

Potentiometric perchlorate determination at nanomolar concentrations in vegetables.

PubMed

Leoterio, Dilmo M S; Paim, Ana Paula S; Belian, Mônica F; Galembeck, André; Lavorante, André F; Pinto, Edgar; Amorim, Célia G; Araújo, Alberto N; Montenegro, Maria C B S M

2017-07-15

In this work, an expeditious method based on the multi-commutated flow-analysis concept with potentiometric detection is proposed to perform determinations of the emergent contaminant perchlorate in vegetable matrices down to nanomolar concentration. To accomplish the task, a tubular shaped potentiometric sensor selective to perchlorate ion was constructed with a PVC membrane containing 12mmol/kg of the polyamine bisnaphthalimidopropyl-4,4'-diaminodiphenylmethane and 2-nitrophenyl phenyl ether 68% (w/w) as plasticizer casted on a conductive epoxy resin. Under optimal flow conditions, the sensor responded linearly in the concentration range of 6.3×10 -7 -1.0×10 -3 mol/L perchlorate. In order to extend the determinations to lower concentrations (4.6(±1.3)×10 -10 mol/L perchlorate), a column packed with 70mg of sodium 2,5,8,11,14-pentaoxa-1-silacyclotetradecane-polymer was coupled to the flow-system thus enabling prior pre-concentration of the perchlorate. The proposed procedure provides a simpler alternative for the determination of perchlorate in foods, nowadays only allowed by sophisticated and expensive equipment and laborious methods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of complex dissociative disorder patients and simulated dissociation in forensic contexts.

PubMed

Brand, Bethany L; Webermann, Aliya R; Frankel, A Steven

Few assessors receive training in assessing dissociation and complex dissociative disorders (DDs). Potential differential diagnoses include anxiety, mood, psychotic, substance use, and personality disorders, as well as exaggeration and malingering. Individuals with DDs typically elevate on many clinical and validity scales on psychological tests, yet research indicates that they can be distinguished from DD simulators. Becoming informed about the testing profiles of DD individuals and DD simulators can improve the accuracy of differential diagnoses in forensic settings. In this paper, we first review the testing profiles of individuals with complex DDs and contrast them with DD simulators on assessment measures used in forensic contexts, including the Minnesota Multiphasic Personality Inventory-2 (MMPI-2), Personality Assessment Inventory (PAI), and the Structured Inventory of Reported Symptoms (SIRS), as well as dissociation-specific measures such as the Dissociative Experiences Scale (DES) and Structured Clinical Interview for DSM-IV Dissociative Disorders (SCID-D-R). We then provide recommendations for assessing complex trauma and dissociation through the aforementioned assessments. Copyright © 2016 Elsevier Ltd. All rights reserved.

A chemical model of seawater including dissolved ammonia and the stoichiometric dissociation constant of ammonia in estuarine water and seawater from -2 to 40°C

NASA Astrophysics Data System (ADS)

Clegg, Simon L.; Whitfield, Michael

1995-06-01

The calculation of the percentage of un-ionised ammonia in estuarine water and seawater requires values of the stoichiometric dissociation constant of ammonia, defined by: K*a/mol kg -1 = mNH 3mH +/ mNH +4, where m denotes molality. A thermodynamic model of seawater, including dissolved NH 3 and NH +4, is developed using an extended Pitzer formalism parameterised from available data. The model is validated using emf measurements for cells containing artificial seawater with added HCl, and NH 4Cl, and NH 3 over a range of temperatures and salinities. Calculated values of K*a are tabulated from 0 to 40 ppt salinity and -2 to 40°C, on both a free ( mH +) and total ( mH + + mHSO -4) hydrogen ion basis for use with pH measurements made on the corresponding scales. Accuracy (in K*a) is likely to be better than 5% at all temperatures and salinities.

Use of an exchange method to estimate the association and dissociation rate constants of cadmium complexes formed with low-molecular-weight organic acids commonly exuded by plant roots.

PubMed

Schneider, André; Nguyen, Christophe

2011-01-01

Organic acids released from plant roots can form complexes with cadmium (Cd) in the soil solution and influence metal bioavailability not only due to the nature and concentration of the complexes but also due to their lability. The lability of a complex influences its ability to buffer changes in the concentration of free ions (Cd); it depends on the association (, m mol s) and dissociation (, s) rate constants. A resin exchange method was used to estimate and (m mol s), which is the conditional estimate of depending on the calcium (Ca) concentration in solution. The constants were estimated for oxalate, citrate, and malate, three low-molecular-weight organic acids commonly exuded by plant roots and expected to strongly influence Cd uptake by plants. For all three organic acids, the and estimates were around 2.5 10 m mol s and 1.3 × 10 s, respectively. Based on the literature, these values indicate that the Cd- low-molecular-weight organic acids complexes formed between Cd and low-molecular-weight organic acids may be less labile than complexes formed with soil soluble organic matter but more labile than those formed with aminopolycarboxylic chelates. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Water-Soluble Nanoparticle Receptors Supramolecularly Coded for Acidic Peptides.

PubMed

Fa, Shixin; Zhao, Yan

2018-01-02

Sequence-specific recognition of peptides is of enormous importance to many chemical and biological applications, but has been difficult to achieve due to the minute differences in the side chains of amino acids. Acidic peptides are known to play important roles in cell growth and gene expression. In this work, we report molecularly imprinted micelles coded with molecular recognition information for the acidic and hydrophobic side chains of acidic peptides. The imprinted receptors could distinguish acidic amino acids from other polar and nonpolar amino acids, with dissociation constants of tens of nanomolar for biologically active peptides containing up to 18 amino acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Translating Hysteria: PTSD dissociative subtype].

PubMed

Levy Yeyati, Elena

2016-03-01

To address the symptoms of depersonalization and derealization a specific dissociative subtype of posttraumatic stress disorder has been included in DSM-5. Depersonalization and derealization have been defined as acute and chronic symptoms of dissociative disorders since DSM-III. Dissociative disorders with chronic features are often diagnosed in North America, Canada and other European countries, but this is not the case in Argentina. Dissociative disorders have clinical and historical features that are strongly connected with hysteria. The latter is included in ICD-10 within the guidelines for diagnoses of dissociative disorders. This would be one of the reasons for not using dissociative disorders with chronic presentations of symptoms like depersonalization and derealization in countries other than North America or Canada: instead hysteria keeps on been used. The relation between trauma, dissociation and hysteria has been explained in different ways depending on the underlying theory (i.e. Janet's or Freud's). Janet's conceptualizations have had decisive influence in DSM formulations in chronic forms of dissociative disorders. Janet's and Freud's theories lead to different consequences on psychotherapy: hypnosis or psychoanalysis. The aim of this article is to show that the authors of PTSD dissociative subtype are in search of a cross-cultural validity of the construct which might be able to exert a more global influence.

[Dissociative disorders and affective disorders].

PubMed

Montant, J; Adida, M; Belzeaux, R; Cermolacce, M; Pringuey, D; Da Fonseca, D; Azorin, J-M

2014-12-01

The phenomenology of dissociative disorders may be complex and sometimes confusing. We describe here two cases who were initially misdiagnosed. The first case concerned a 61 year-old woman, who was initially diagnosed as an isolated dissociative fugue and was actually suffering from severe major depressive episode. The second case concerned a 55 year-old man, who was suffering from type I bipolar disorder and polyvascular disease, and was initially diagnosed as dissociative fugue in a mooddestabilization context, while it was finally a stroke. Yet dissociative disorders as affective disorder comorbidity are relatively unknown. We made a review on this topic. Dissociative disorders are often studied through psycho-trauma issues. Litterature is rare on affective illness comorbid with dissociative disorders, but highlight the link between bipolar and dissociative disorders. The later comorbidity often refers to an early onset subtype with also comorbid panic and depersonalization-derealization disorder. Besides, unipolar patients suffering from dissociative symptoms have more often cyclothymic affective temperament. Despite the limits of such studies dissociative symptoms-BD association seems to correspond to a clinical reality and further works on this topic may be warranted. Copyright © 2014 L’Encéphale. Published by Elsevier Masson SAS.. All rights reserved.

IMBALANCE OF DNA METHYLATION, BOTH HYPERMETHYLATION AND HYPOMETHYLATION, OCCUR AFTER EXPOSURE OF HUMAN CELLS TO NANOMOLAR CONCENTRATIONS OF ARSENITE IN CULTURE.

EPA Science Inventory

Imbalance of DNA methylation, BOTH hypermethylation and hypomethylation, occur after exposure of human cells to nanomolar concentrations of arsenite in culture.

We and others have hypothesized that a mechanism of arsenic carcinogenesis could involve alteration of DNA methy...

Nanomolar detection of hypochlorite by a rhodamine-based chiral hydrazide in absolute aqueous media: application in tap water analysis with live-cell imaging.

PubMed

Goswami, Shyamaprosad; Das, Avijit Kumar; Manna, Abhishek; Maity, Anup Kumar; Saha, Partha; Quah, Ching Kheng; Fun, Hoong-Kun; Abdel-Aziz, Hatem A

2014-07-01

By employing the oxidation property of hypochlorite (OCl(-)), a novel rhodamine-based hydrazide of the chiral acid ((S)-(-)-2-pyrrolidone-5-carboxylic acid) (RHHP) was designed and synthesized for detection of OCl(-) absolutely in aqueous medium at nanomolar level. The structure of the chiral sensor was also proved by the X-ray crystallography. The bioactivity and the application of the probe for detection of OCl(-) in natural water system have been demonstrated. A plausible mechanism for oxidation of the sensor followed by hydrolysis is also proposed. The sensibility of the receptor toward OCl(-) was studied in absolute aqueous media, and the detection limit of hypochlorite-mediated oxidation to the receptor in nanomolar level makes this platform (RHHP) an ultrasensitive and unique system for OCl(-) oxidation.

[Dissociated learning with GABAergic drugs].

PubMed

Azarashvili, A A; Kaĭmachnikova, I E

2008-01-01

The possibility of dissociated learning was investigated using drugs which act directly on GABAB receptors of the brain. The earlier proposed suggestion that the cholinergic system plays a key role in the mechanisms of dissociated learning was tested. It was shown in male Wistar rats that dissociated learning was possible with GABAergic drugs. The dissociated state was induced by injecting the animals with both GABA agonist Baclofen and GABA antagonist 5-aminovaleric acid. Thus, dissociated learning is possible with drugs which act on either cholinergic or GABAergic transmitter systems.

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.

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

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.

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.

Pair interactions in polyelectrolyte-nanoparticle systems: Influence of dielectric inhomogeneities and the partial dissociation of polymers and nanoparticles.

PubMed

Pryamitsyn, Victor; Ganesan, Venkat

2015-10-28

We study the effective pair interactions between two charged spherical particles in polyelectrolyte solutions using polymer self-consistent field theory. In a recent study [V. Pryamitsyn and V. Ganesan, Macromolecules 47, 6095 (2015)], we considered a model in which the particles possess fixed charge density, the polymers contain a prespecified amount of dissociated charges and, the dielectric constant of the solution was assumed to be homogeneous in space and independent of the polymer concentration. In this article, we present results extending our earlier model to study situations in which either or both the particle and the polymers possess partially dissociable groups. Additionally, we also consider the case when the dielectric constant of the solution depends on the local concentration of the polymers and when the particle's dielectric constant is lower than that of the solvent. For each case, we quantify the polymer-mediated interactions between the particles as a function of the polymer concentrations and the degree of dissociation of the polymer and particles. Consistent with the results of our previous study, we observe that the polymer-mediated interparticle interactions consist of a short-range attraction and a long-range repulsion. The partial dissociablity of the polymer and particles was seen to have a strong influence on the strength of the repulsive portion of the interactions. Rendering the dielectric permittivity to be inhomogeneous has an even stronger effect on the repulsive interactions and results in changes to the qualitative nature of interactions in some parametric ranges.

Selecting for Fast Protein-Protein Association As Demonstrated on a Random TEM1 Yeast Library Binding BLIP.

PubMed

Cohen-Khait, Ruth; Schreiber, Gideon

2018-04-27

Protein-protein interactions mediate the vast majority of cellular processes. Though protein interactions obey basic chemical principles also within the cell, the in vivo physiological environment may not allow for equilibrium to be reached. Thus, in vitro measured thermodynamic affinity may not provide a complete picture of protein interactions in the biological context. Binding kinetics composed of the association and dissociation rate constants are relevant and important in the cell. Therefore, changes in protein-protein interaction kinetics have a significant impact on the in vivo activity of the proteins. The common protocol for the selection of tighter binders from a mutant library selects for protein complexes with slower dissociation rate constants. Here we describe a method to specifically select for variants with faster association rate constants by using pre-equilibrium selection, starting from a large random library. Toward this end, we refine the selection conditions of a TEM1-β-lactamase library against its natural nanomolar affinity binder β-lactamase inhibitor protein (BLIP). The optimal selection conditions depend on the ligand concentration and on the incubation time. In addition, we show that a second sort of the library helps to separate signal from noise, resulting in a higher percent of faster binders in the selected library. Fast associating protein variants are of particular interest for drug development and other biotechnological applications.

Is the dissociative adult suggestible? A test of the trauma and fantasy models of dissociation.

PubMed

Kluemper, Nicole S; Dalenberg, Constance

2014-01-01

Psychologists have long assumed a connection between traumatic experience and psychological dissociation. This hypothesis is referred to as the trauma model of dissociation. In the past decade, a series of papers have been published that question this traditional causal link, proposing an alternative fantasy model of dissociation. In the present research, the relationship among dissociation, suggestibility, and fantasy proneness was examined. Suggestibility was measured through the Gudjonsson Scale of Interrogative Suggestibility (GSS) as well as an autobiographically based version of this measure based on the events of September 11, 2001. Consistent with prior research and with the trauma model, dissociation correlated positively with trauma severity (r = .32, p < .01) and fantasy proneness (r = .60, p < .01). Inconsistent with the fantasy model, dissociation did not correlate with the neutral form of the GSS and correlated negatively (r = -.24, p < .05) with the trauma-focused form of this suggestibility measure. Although some participants did become quite emotional during the procedure, the risk/benefit ratio was perceived by almost all participants to be positive, with more reactive individuals evaluating the procedure more positively. The results consistently support the trauma model of dissociation and fail to support the fantasy model of dissociation.

Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biderman, N. J.; Sundaramoorthy, R.; Haldar, Pradeep

We conducted two sets of diffusion-reaction numerical simulations using a finite difference method (FDM) in order to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,Ga)Se 2 (CIGS) and Cu 2ZnSn(S, Se) 4 (CZTSSe or CZTS) via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases themore » equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. And according to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.« less

Dissociative diffusion mechanism in vacancy-rich materials according to mass action kinetics

DOE PAGES

Biderman, N. J.; Sundaramoorthy, R.; Haldar, Pradeep; ...

2016-05-13

We conducted two sets of diffusion-reaction numerical simulations using a finite difference method (FDM) in order to investigate fast impurity diffusion via interstitial sites in vacancy-rich materials such as Cu(In,Ga)Se 2 (CIGS) and Cu 2ZnSn(S, Se) 4 (CZTSSe or CZTS) via the dissociative diffusion mechanism where the interstitial diffuser ultimately reacts with a vacancy to produce a substitutional. The first set of simulations extends the standard interstitial-limited dissociative diffusion theory to vacancy-rich material conditions where vacancies are annihilated in large amounts, introducing non-equilibrium vacancy concentration profiles. The second simulation set explores the vacancy-limited dissociative diffusion where impurity incorporation increases themore » equilibrium vacancy concentration. In addition to diffusion profiles of varying concentrations and shapes that were obtained in all simulations, some of the profiles can be fitted with the constant- and limited-source solutions of Fick’s second law despite the non-equilibrium condition induced by the interstitial-vacancy reaction. The first set of simulations reveals that the dissociative diffusion coefficient in vacancy-rich materials is inversely proportional to the initial vacancy concentration. In the second set of numerical simulations, impurity-induced changes in the vacancy concentration lead to distinctive diffusion profile shapes. The simulation results are also compared with published data of impurity diffusion in CIGS. And according to the characteristic properties of diffusion profiles from the two set of simulations, experimental detection of the dissociative diffusion mechanism in vacancy-rich materials may be possible.« less

Direction-dependent force-induced dissociation dynamics of an entropic-driven lock-and-key assembly.

PubMed

Chen, Yen-Fu; Chen, Hsuan-Yi; Sheng, Yu-Jane; Tsao, Heng-Kwong

2017-09-01

The unbinding dynamics of a nanosized sphere-and-cavity assembly under the pulling of constant force and constant loading rate is explored by dissipative particle dynamics simulations. The formation of this matched lock-and-key pair in a polymer solution is driven by the depletion attraction. The two-dimensional free energy landscape U(x,z) associated with this assembly is constructed. Our results indicate that the unbinding pathway along the orientation of the assembly is unfavorable due to the relatively high energy barrier compared to that along the tortuous minimum path whose energy barrier is not high. It is also found that the dissociation rate depends on the direction of the external force (θ) with respect to the assembly orientation. The presence of the force component perpendicular to the assembly orientation can reduce the bond lifetime significantly by driving the key particle to approach the minimum path. Moreover, the dissociation dynamics can be facilitated even by a pushing force compared to the spontaneous dissociation (without forces). To elucidate the effective pathway under pulling, the escaping position is analyzed and its mean direction with respect to the assembly orientation rises generally with increasing θ, revealing that the presence of the force component along the minimum pathway is helpful. The importance of the direction of the external pulling has been demonstrated in our simple system. Therefore, this effect should be considered in more complicated unbinding experiments.

Direction-dependent force-induced dissociation dynamics of an entropic-driven lock-and-key assembly

NASA Astrophysics Data System (ADS)

Chen, Yen-Fu; Chen, Hsuan-Yi; Sheng, Yu-Jane; Tsao, Heng-Kwong

2017-09-01

The unbinding dynamics of a nanosized sphere-and-cavity assembly under the pulling of constant force and constant loading rate is explored by dissipative particle dynamics simulations. The formation of this matched lock-and-key pair in a polymer solution is driven by the depletion attraction. The two-dimensional free energy landscape U (x ,z ) associated with this assembly is constructed. Our results indicate that the unbinding pathway along the orientation of the assembly is unfavorable due to the relatively high energy barrier compared to that along the tortuous minimum path whose energy barrier is not high. It is also found that the dissociation rate depends on the direction of the external force (θ ) with respect to the assembly orientation. The presence of the force component perpendicular to the assembly orientation can reduce the bond lifetime significantly by driving the key particle to approach the minimum path. Moreover, the dissociation dynamics can be facilitated even by a pushing force compared to the spontaneous dissociation (without forces). To elucidate the effective pathway under pulling, the escaping position is analyzed and its mean direction with respect to the assembly orientation rises generally with increasing θ , revealing that the presence of the force component along the minimum pathway is helpful. The importance of the direction of the external pulling has been demonstrated in our simple system. Therefore, this effect should be considered in more complicated unbinding experiments.

Dissociation of Laboratory-Synthesized Methane Hydrate in Coarse-Grained Sediments by Slow Depressurization

NASA Astrophysics Data System (ADS)

Phillips, S. C.; You, K.; Borgfeldt, T.; Meyer, D.; Dong, T.; Flemings, P. B.

2016-12-01

We performed four dissociation experiments in which experimentally-formed methane hydrate was dissociated via slow, stepwise depressurization, revealing in situ salinity conditions. Overall, these results suggest the occurrence of local pore water freshening around dissociating hydrate in which bulk equilibrium behavior is limited by salt diffusion. Depressurization was performed at a constant confining temperature over 1 to 3 weeks by releasing small volumes of methane gas from the top of a vertically-oriented sample into an inverted graduated cylinder. We identify three distinct regimes of depressurization based on pressure drop behavior: (1) release of free gas down to initial hydrate dissociation at 3.3 MPa in NaBr or 4.64 MPa in NaCl, (2) dissociation of methane hydrate characterized by a slow, logarithmic increase in pressure after each gas release and (3) residual free gas release. Initial hydrate dissociation in NaCl brine at 4.64 MPa corresponds to the phase boundary for hydrate in 9.6 wt% NaCl. In the NaCl experiment, pressure increases of 0.16 MPa while the sample was shut in over 3 days likely correspond to a recovery in salinity of 0.7 wt. %. Salt ions likely diffuse from brine ahead of the hydrate front, based on a length scale for diffusion of NaCl of 6.3 cm for 3 days. In this experiment dissociation at bulk equilibrium is expected to decline from 4.54 to 4.04 MPa; however actual dissociation during 73 gas releases over 15 days, results in a pressure drop from 4.64 to 3.25 MPa. Hydrate samples were formed by injection of methane gas at 1 ºC and 12.24 MPa within a cylinder packed with medium-grained quartz sand and initially saturated in a 7 wt% NaBr or NaCl solution. In two experiments in which the system was thoroughly leak tested, total methane consumed during formation and recovered during depressurization match within 7% indicating this approach to be relatively accurate for determining total methane in experimental or pressure core samples.

Dissociative Identity Disorder

PubMed Central

2009-01-01

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. PMID:19724751

Low-energy collision induced dissociation (low-energy CID), collision induced dissociation (CID) and higher-energy collision dissociation (HCD) mass spectrometry for structural elucidation of saccharides and clarification of their dissolution mechanism in DMAc/LiCl.

PubMed

Bayat, Parisa; Lesage, Denis; Cole, Richard B

2018-05-29

The dissolution mechanism of oligosaccharides in N,N-dimethylacetamide/lithium chloride (DMAc/LiCl), a solvent used for cellulose dissolution, and the capabilities of low-energy collision induced dissociation (low-energy CID), collision induced dissociation (CID) and higher-energy collision dissociation (HCD) for structural analysis of carbohydrates were investigated. Comparing the spectra obtained using three techniques shows that, generally, when working with mono-lithiated sugars, CID spectra provide more structurally informative fragments, and glycosidic bond cleavage is the main pathway. However, when working with di-lithiated sugars, HCD spectra can be more informative providing predominately cross-ring cleavage fragments. This is because HCD is a non-resonant activation technique and it allows a higher amount of energy to be deposited in a short time, giving access to more endothermic decomposition pathways as well as consecutive fragmentations. The difference in preferred dissociation pathways of mono-lithiated and di-lithiated sugars indicates that the presence of the second lithium strongly influences the relative rate constants for cross-ring cleavages (rearrangement) vs. direct glycosidic bond cleavages, and disfavors the latter. Regarding the dissolution mechanism of sugars in DMAc/LiCl, CID and HCD experiments on di-lithiated and tri-lithiated sugars reveal that intensities of product ions containing two Li + or three Li + , respectively, are higher than those bearing only one Li + . In addition, comparing the fragmentation spectra (both HCD and CID) of LiCl adducted lithiated sugar and NaCl adducted sodiated sugar shows that while, in the latter case, loss of NaCl is dominant, in the former case, loss of HCl occurs preferentially. The compiled evidence implies that there is a strong and direct interaction between lithium and the saccharide during the dissolution process in the DMAc/LiCl solvent system. This article is protected by copyright. All

Dissociated learning using GABAergic drugs.

PubMed

Azarashvili, A A; Kaimachnikova, I E

2009-02-01

Experiments on Wistar rats addressed the possibility of dissociated learning using drugs acting directly on brain GABA(B) receptors. A previously suggested hypothesis was tested: that the cholinergic system of the brain plays the decisive role in the mechanisms of dissociative learning. The data obtained here provided evidence that dissociated learning an occur with compounds acting on the GABAergic transmitter system of the brain. Dissociated states arose on treatment of animals with both the GABA-mimetic baclofen and the GABA receptor antagonist 5-aminovaleric acid. Thus, these results show that dissociated learning can occur using drugs acting on both the cholinergic and the GABAergic transmitter systems of the brain.

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". Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Dissociative symptoms and dissociative disorders comorbidity in obsessive compulsive disorder: Symptom screening, diagnostic tools and reflections on treatment

PubMed Central

Belli, Hasan

2014-01-01

Borderline personality disorder, conversion disorder and obsessive compulsive disorder frequently have dissociative symptoms. The literature has demonstrated that the level of dissociation might be correlated with the severity of obsessive compulsive disorder (OCD) and that those not responding to treatment had high dissociative symptoms. The structured clinical interview for DSM-IV dissociative disorders, dissociation questionnaire, somatoform dissociation questionnaire and dissociative experiences scale can be used for screening dissociative symptoms and detecting dissociative disorders in patients with OCD. However, a history of neglect and abuse during childhood is linked to a risk factor in the pathogenesis of dissociative psychopathology in adults. The childhood trauma questionnaire-53 and childhood trauma questionnaire-40 can be used for this purpose. Clinicians should not fail to notice the hidden dissociative symptoms and childhood traumatic experiences in OCD cases with severe symptoms that are resistant to treatment. Symptom screening and diagnostic tools used for this purpose should be known. Knowing how to treat these pathologies in patients who are diagnosed with OCD can be crucial. PMID:25133142

Dissociative symptoms and dissociative disorders comorbidity in obsessive compulsive disorder: Symptom screening, diagnostic tools and reflections on treatment.

PubMed

Belli, Hasan

2014-08-16

Borderline personality disorder, conversion disorder and obsessive compulsive disorder frequently have dissociative symptoms. The literature has demonstrated that the level of dissociation might be correlated with the severity of obsessive compulsive disorder (OCD) and that those not responding to treatment had high dissociative symptoms. The structured clinical interview for DSM-IV dissociative disorders, dissociation questionnaire, somatoform dissociation questionnaire and dissociative experiences scale can be used for screening dissociative symptoms and detecting dissociative disorders in patients with OCD. However, a history of neglect and abuse during childhood is linked to a risk factor in the pathogenesis of dissociative psychopathology in adults. The childhood trauma questionnaire-53 and childhood trauma questionnaire-40 can be used for this purpose. Clinicians should not fail to notice the hidden dissociative symptoms and childhood traumatic experiences in OCD cases with severe symptoms that are resistant to treatment. Symptom screening and diagnostic tools used for this purpose should be known. Knowing how to treat these pathologies in patients who are diagnosed with OCD can be crucial.

Molybdenum-carbon bond dissociation energies in Mo(CO) sub 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganske, J.A.; Rosenfeld, R.N.

1990-05-17

The pressure dependence of the recombination rate constants for Mo(CO){sub n} (n = 3,4 and 5) with CO has been studied by time-resolved infrared laser absorption spectroscopy. These data, in conjunction with an RRKM model for unimolecular decay of the activated molecules (Mo(CO){sub 6})*, (Mo(CO){sub 5})*, and (Mo(CO){sub 4})*, have allowed the determination of the bond dissociation energies for several of the Mo-C bonds in Mo(CO){sub 6}. The first Mo-C bond dissociation energies for Mo(CO){sub 6}, Mo(CO){sub 5}, and Mo(CO){sub 4} are found to be DH{degree}((CO){sub 5}Mo{hor ellipsis}CO) = 35 {plus minus} 5 kcal/mol, DH{degree}((CO){sub 4}Mo{hor ellipsis}CO) = 27 {plusmore » minus} 5 kcal/mol, and DH{degree}((CO){sub 3}Mo{hor ellipsis}CO) = 31 {plus minus} 5 kcal/mol.« less

Dissociative experiences in patients with epilepsy.

PubMed

Özdemir, Osman; Cilingir, Vedat; Özdemir, Pınar Güzel; Milanlioglu, Aysel; Hamamci, Mehmet; Yilmaz, Ekrem

2016-03-01

A few studies have explored dissociative experiences in epilepsy patients. We investigated dissociative experiences in patients with epilepsy using the dissociative experiences scale (DES). Ninety-eight patients with epilepsy and sixty healthy controls were enrolled in this study. A sociodemographic questionnaire and the Dissociative Experiences Scale (DES), Beck Depression Inventory (BDI) and Beck Anxiety Inventory (BAI) were administered to the participants. The DES scores were significantly higher for the patients with epilepsy than the healthy individuals. The number of individuals with pathological dissociation (DES ≥ 30) was higher in the epilepsy group (n = 28) than in the control group (n = 8). Also, higher levels of dissociation were significantly associated with frequency of seizures, but were not associated with duration of epilepsy and age at onset of the disorder. These findings demonstrate that patients with epilepsy are more prone to dissociation than controls. The high rate of dissociative experiences among patients with epilepsy suggest that some epilepsy-related factors are present.

Determination of dissociation constant of the NFκB p50/p65 heterodimer using fluorescence cross-correlation spectroscopy in the living cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tiwari, Manisha; Mikuni, Shintaro; Muto, Hideki

Highlights: •We used two-laser-beam FCCS to determine the dissociation constant (K{sub d}) of IPT domain of p50/p65 heterodimer in living cell. •Interaction of p50 and p65 was analyzed in the cytoplasm and nucleus of single living cell. •Binding affinity of p50/p65 heterodimer is higher in cytoplasm than that of nucleus. -- Abstract: Two-laser-beam fluorescence cross-correlation spectroscopy (FCCS) is promising technique that provides quantitative information about the interactions of biomolecules. The p50/p65 heterodimer is the most abundant and well understood of the NFκB dimers in most cells. However, the quantitative value of affinity, namely the K{sub d}, for the heterodimer inmore » living cells is not known yet. To quantify the heterodimerization of the IPT domain of p50/p65 in the living cell, we used two-laser-beam FCCS. The K{sub d} values of mCherry{sub 2}- and EGFP-fused p50 and p65 were determined to be 0.46 μM in the cytoplasm and 1.06 μM in the nucleus of the living cell. These results suggest the different binding affinities of the p50/p65 heterodimer in the cytoplasm and nucleus of the living cell and different complex formation in each region.« less

Ab initio state-specific N2 + O dissociation and exchange modeling for molecular simulations

NASA Astrophysics Data System (ADS)

Luo, Han; Kulakhmetov, Marat; Alexeenko, Alina

2017-02-01

Quasi-classical trajectory (QCT) calculations are used in this work to calculate state-specific N2(X1Σ ) +O(3P ) →2 N(4S ) +O(3P ) dissociation and N2(X1Σ ) +O(3P ) →NO(X2Π ) +N(4S ) exchange cross sections and rates based on the 13A″ and 13A' ab initio potential energy surface by Gamallo et al. [J. Chem. Phys. 119, 2545-2556 (2003)]. The calculations consider translational energies up to 23 eV and temperatures between 1000 K and 20 000 K. Vibrational favoring is observed for dissociation reaction at the whole range of collision energies and for exchange reaction around the dissociation limit. For the same collision energy, cross sections for v = 30 are 4 to 6 times larger than those for the ground state. The exchange reaction has an effective activation energy that is dependent on the initial rovibrational level, which is different from dissociation reaction. In addition, the exchange cross sections have a maximum when the total collision energy (TCE) approaches dissociation energy. The calculations are used to generate compact QCT-derived state-specific dissociation (QCT-SSD) and QCT-derived state-specific exchange (QCT-SSE) models, which describe over 1 × 106 cross sections with about 150 model parameters. The models can be used directly within direct simulation Monte Carlo and computational fluid dynamics simulations. Rate constants predicted by the new models are compared to the experimental measurements, direct QCT calculations and predictions by other models that include: TCE model, Bose-Candler QCT-based exchange model, Macheret-Fridman dissociation model, Macheret's exchange model, and Park's two-temperature model. The new models match QCT-calculated and experimental rates within 30% under nonequilibrium conditions while other models under predict by over an order of magnitude under vibrationally-cold conditions.

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.

Pentamidine Is Not a Permeant but a Nanomolar Inhibitor of the Trypanosoma brucei Aquaglyceroporin-2.

PubMed

Song, Jie; Baker, Nicola; Rothert, Monja; Henke, Björn; Jeacock, Laura; Horn, David; Beitz, Eric

2016-02-01

The chemotherapeutic arsenal against human African trypanosomiasis, sleeping sickness, is limited and can cause severe, often fatal, side effects. One of the classic and most widely used drugs is pentamidine, an aromatic diamidine compound introduced in the 1940s. Recently, a genome-wide loss-of-function screen and a subsequently generated trypanosome knockout strain revealed a specific aquaglyceroporin, TbAQP2, to be required for high-affinity uptake of pentamidine. Yet, the underlying mechanism remained unclear. Here, we show that TbAQP2 is not a direct transporter for the di-basic, positively charged pentamidine. Even though one of the two common cation filters of aquaglyceroporins, i.e. the aromatic/arginine selectivity filter, is unconventional in TbAQP2, positively charged compounds are still excluded from passing the channel. We found, instead, that the unique selectivity filter layout renders pentamidine a nanomolar inhibitor of TbAQP2 glycerol permeability. Full, non-covalent inhibition of an aqua(glycero)porin in the nanomolar range has not been achieved before. The remarkable affinity derives from an electrostatic interaction with Asp265 and shielding from water as shown by structure-function evaluation and point mutation of Asp265. Exchange of the preceding Leu264 to arginine abolished pentamidine-binding and parasites expressing this mutant were pentamidine-resistant. Our results indicate that TbAQP2 is a high-affinity receptor for pentamidine. Taken together with localization of TbAQP2 in the flagellar pocket of bloodstream trypanosomes, we propose that pentamidine uptake is by endocytosis.

Multiphoton dissociation and thermal unimolecular reactions induced by infrared lasers. [REAMPA code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, H.L.

1981-04-01

Multiphoton dissociation (MPD) of ethyl chloride was studied using a tunable 3.3 ..mu..m laser to excite CH stretches. The absorbed energy increases almost linearly with fluence, while for 10 ..mu..m excitation there is substantial saturation. Much higher dissociation yields were observed for 3.3 ..mu..m excitation than for 10 ..mu..m excitation, reflecting bottlenecking in the discrete region of 10 ..mu..m excitation. The resonant nature of the excitation allows the rate equations description for transitions in the quasicontinuum and continuum to be extended to the discrete levels. Absorption cross sections are estimated from ordinary ir spectra. A set of cross sections whichmore » is constant or slowly decreasing with increasing vibrational excitation gives good fits to both absorption and dissociation yield data. The rate equations model was also used to quantitatively calculate the pressure dependence of the MPD yield of SF/sub 6/ caused by vibrational self-quenching. Between 1000-3000 cm/sup -1/ of energy is removed from SF/sub 6/ excited to approx. > 60 kcal/mole by collision with a cold SF/sub 6/ molecule at gas kinetic rate. Calculation showed the fluence dependence of dissociation varies strongly with the gas pressure. Infrared multiphoton excitation was applied to study thermal unimolecular reactions. With SiF/sub 4/ as absorbing gas for the CO/sub 2/ laser pulse, transient high temperature pulses were generated in a gas mixture. IR fluorescence from the medium reflected the decay of the temperature. The activation energy and the preexponential factor of the reactant dissociation were obtained from a phenomenological model calculation. Results are presented in detail. (WHK)« less

Trends in electron-ion dissociative recombination of benzene analogs with functional group substitutions: Negative Hammett σpara values

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick Andrew; Adams, Nigel; Dotan, Itzhak

2014-06-01

An in-depth study of the effects of functional group substitution on benzene's electron-ion dissociative recombination (e-IDR) rate constant has been conducted. The e-IDR rate constants for benzene, biphenyl, toluene, ethylbenzene, anisole, phenol, and aniline have been measured using a Flowing Afterglow equipped with an electrostatic Langmuir probe (FALP). These measurements have been made over a series of temperatures from 300 to 550 K. A relationship between the Hammett σpara values for each compound and rate constant has indicated a trend in the e-IDR rate constants and possibly in their temperature dependence data. The Hammett σpara value is a method to describe the effect a functional group substituted to a benzene ring has upon the reaction rate constant.

Isotherm-Based Thermodynamic Models for Solute Activities of Organic Acids with Consideration of Partial Dissociation.

PubMed

Nandy, Lucy; Ohm, Peter B; Dutcher, Cari S

2016-06-23

Organic acids make up a significant fraction of the organic mass in atmospheric aerosol particles. The calculation of gas-liquid-solid equilibrium partitioning of the organic acid is therefore critical for accurate determination of atmospheric aerosol physicochemical properties and processes such as new particle formation and activation to cloud condensation nuclei. Previously, an adsorption isotherm-based statistical thermodynamic model was developed for capturing solute concentration-activity relationships for multicomponent aqueous solutions over the entire concentration range (Dutcher et al. J. Phys. Chem. C/A 2011, 2012, 2013), with model parameters for energies of adsorption successfully related to dipole-dipole electrostatic forces in solute-solvent and solvent-solvent interactions for both electrolytes and organics (Ohm et al. J. Phys. Chem. A 2015). However, careful attention is needed for weakly dissociating semivolatile organic acids. Dicarboxylic acids, such as malonic acid and glutaric acid are treated here as a mixture of nondissociated organic solute (HA) and dissociated solute (H(+) + A(-)). It was found that the apparent dissociation was greater than that predicted by known dissociation constants alone, emphasizing the effect of dissociation on osmotic and activity coefficient predictions. To avoid additional parametrization from the mixture approach, an expression was used to relate the Debye-Hückel hard-core collision diameter to the adjustable solute-solvent intermolecular distance. An improved reference state treatment for electrolyte-organic aqueous mixtures, such as that observed here with partial dissociation, has also been proposed. This work results in predictive correlations for estimation of organic acid and water activities for which there is little or no activity data.

Experimentally-induced dissociation impairs visual memory.

PubMed

Brewin, Chris R; Mersaditabari, Niloufar

2013-12-01

Dissociation is a phenomenon common in a number of psychological disorders and has been frequently suggested to impair memory for traumatic events. In this study we explored the effects of dissociation on visual memory. A dissociative state was induced experimentally using a mirror-gazing task and its short-term effects on memory performance were investigated. Sixty healthy individuals took part in the experiment. Induced dissociation impaired visual memory performance relative to a control condition; however, the degree of dissociation was not associated with lower memory scores in the experimental group. The results have theoretical and practical implications for individuals who experience frequent dissociative states such as patients with posttraumatic stress disorder (PTSD). Copyright © 2013 Elsevier Inc. All rights reserved.

Speech-Language Dissociations, Distractibility, and Childhood Stuttering

PubMed Central

Conture, Edward G.; Walden, Tedra A.; Lambert, Warren E.

2015-01-01

Purpose This study investigated the relation among speech-language dissociations, attentional distractibility, and childhood stuttering. Method Participants were 82 preschool-age children who stutter (CWS) and 120 who do not stutter (CWNS). Correlation-based statistics (Bates, Appelbaum, Salcedo, Saygin, & Pizzamiglio, 2003) identified dissociations across 5 norm-based speech-language subtests. The Behavioral Style Questionnaire Distractibility subscale measured attentional distractibility. Analyses addressed (a) between-groups differences in the number of children exhibiting speech-language dissociations; (b) between-groups distractibility differences; (c) the relation between distractibility and speech-language dissociations; and (d) whether interactions between distractibility and dissociations predicted the frequency of total, stuttered, and nonstuttered disfluencies. Results More preschool-age CWS exhibited speech-language dissociations compared with CWNS, and more boys exhibited dissociations compared with girls. In addition, male CWS were less distractible than female CWS and female CWNS. For CWS, but not CWNS, less distractibility (i.e., greater attention) was associated with more speech-language dissociations. Last, interactions between distractibility and dissociations did not predict speech disfluencies in CWS or CWNS. Conclusions The present findings suggest that for preschool-age CWS, attentional processes are associated with speech-language dissociations. Future investigations are warranted to better understand the directionality of effect of this association (e.g., inefficient attentional processes → speech-language dissociations vs. inefficient attentional processes ← speech-language dissociations). PMID:26126203

Modulators of actin-myosin dissociation: basis for muscle type functional differences during fatigue

PubMed Central

Karatzaferi, Christina; Adamek, Nancy

2017-01-01

The muscle types present with variable fatigue tolerance, in part due to the myosin isoform expressed. However, the critical steps that define “fatigability” in vivo of fast vs. slow myosin isoforms, at the molecular level, are not yet fully understood. We examined the modulation of the ATP-induced myosin subfragment 1 (S1) dissociation from pyrene-actin by inorganic phosphate (Pi), pH, and temperature using a specially modified stopped-flow system that allowed fast kinetics measurements at physiological temperature. We contrasted the properties of rabbit psoas (fast) and bovine masseter (slow) myosins (obtained from samples collected from New Zealand rabbits and from a licensed abattoir, respectively, according to institutional and national ethics permits). To identify ATP cycling biochemical intermediates, we assessed ATP binding to a preequilibrated mixture of actomyosin and variable [ADP], pH (pH 7 vs. pH 6.2), and Pi (zero, 15, or 30 added mM Pi) in a range of temperatures (5 to 45°C). Temperature and pH variations had little, if any, effect on the ADP dissociation constant (KADP) for fast S1, but for slow S1, KADP was weakened with increasing temperature or low pH. In the absence of ADP, the dissociation constant for phosphate (KPi) was weakened with increasing temperature for fast S1. In the presence of ADP, myosin type differences were revealed at the apparent phosphate affinity, depending on pH and temperature. Overall, the newly revealed kinetic differences between myosin types could help explain the in vivo observed muscle type functional differences at rest and during fatigue. PMID:28931538

Objective documentation of child abuse and dissociation in 12 murderers with dissociative identity disorder.

PubMed

Lewis, D O; Yeager, C A; Swica, Y; Pincus, J H; Lewis, M

1997-12-01

The skepticism regarding the existence of dissociative identity disorder as well as the abuse that engenders it persists for lack of objective documentation. This is doubly so for the disorder in murderers because of issues of suspected malingering. This article presents objective verification of both dissociative symptoms and severe abuse during childhood in a series of adult murderers with dissociative identity disorder. This study consisted of a review of the clinical records of 11 men and one woman with DSM-IV-defined dissociative identity disorder who had committed murder. Data were gathered from medical, psychiatric, social service, school, military, and prison records and from records of interviews with subjects' family members and others. Handwriting samples were also examined. Data were analyzed qualitatively. Signs and symptoms of dissociative identity disorder in childhood and adulthood were corroborated independently and from several sources in all 12 cases; objective evidence of severe abuse was obtained in 11 cases. The subjects had amnesia for most of the abuse and underreported it. Marked changes in writing style and/or signatures were documented in 10 cases. This study establishes, once and for all, the linkage between early severe abuse and dissociative identity disorder. Further, the data demonstrate that the disorder can be distinguished from malingering and from other disorders. The study shows that it is possible, with great effort, to obtain objective evidence of both the symptoms of dissociative identity disorder and the abuse that engenders it.

Dissociation in the laboratory: a comparison of strategies.

PubMed

Leonard, K N; Telch, M J; Harrington, P J

1999-01-01

Several methods for inducing dissociation in the laboratory were examined in a sample of 78 undergraduate students. Participants scoring high or low on the Dissociative Experiences Scale participated in three dissociation challenge conditions: (a) dot-staring task, (b) administration of pulsed photic and audio stimulation and (c) stimulus deprivation. Participants recorded their dissociative experiences both before and after each of the three challenge conditions. Across conditions, high DES participants reported significantly more dissociative sensations than low DES participants, even after controlling for pre-challenge dissociation. Moreover, regardless of DES status, pulsed photo and audio stimulation produced the greatest level of dissociative symptoms. The findings suggest that the induction of dissociative symptoms in a nonclinical sample is easily accomplished in the laboratory and that those who report more dissociative symptoms in their day-to-day life exhibit more pronounced dissociative symptoms when undergoing dissociative challenge in the laboratory. Implications for the study and treatment of dissociative symptoms are discussed.

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.

Label-free Growth Receptor-2 Detection and Dissociation Constant Assessment in Diluted Human Serum Using a Longitudinal Extension Mode of a Piezoelectric Microcantilever Sensor

PubMed Central

Capobianco, Joseph A.; Shih, Wan Y.; Adams, Gregory P.; Shih, Wei-Heng

2011-01-01

We have investigated real-time, label-free, in-situ detection of human epidermal growth factor receptor 2 (Her2) in diluted serum using the first longitudinal extension mode of a lead zirconate-lead titanate (PZT)/glass piezoelectric microcantilever sensor (PEMS) with H3 single-chain variable fragment (scFv) immobilized on the 3-mercaptopropyltrimethoxysilane (MPS) insulation layer of the PEMS surface. We showed that with the longitudinal extension mode, the PZT/glass PEMS consisting of a 1 mm long and 127 μm thick PZT layer bonded with a 75 μm thick glass layer with a 1.8 mm long glass tip could detect Her2 at a concentration of 6-60 ng/ml (or 0.06-0.6 nM) in diluted human serum, about 100 times lower than the concentration limit obtained using the lower-frequency flexural mode of a similar PZT/glass PEMS. We further showed that with the longitudinal mode, the PZT/glass PEMS determined the equilibrium H3-Her2 dissociation constant Kd to be 3.3±0.3 × 10-8 M consistent with the value, 3.2±0.28 ×10-8 M deduced by the surface plasmon resonance method (BIAcore). PMID:22888196

Dissociative recombination in aeronomy

NASA Technical Reports Server (NTRS)

Fox, J. L.

1989-01-01

The importance of dissociative recombination in planetary aeronomy is summarized, and two examples are discussed. The first is the role of dissociative recombination of N2(+) in the escape of nitrogen from Mars. A previous model is updated to reflect new experimental data on the electronic states of N produced in this process. Second, the intensity of the atomic oxygen green line on the nightside of Venus is modeled. Use is made of theoretical rate coefficients for production of O (1S) in dissociative recombination from different vibrational levels of O2(+).

Quantifying Protein-Ligand Binding Constants using Electrospray Ionization Mass Spectrometry: A Systematic Binding Affinity Study of a Series of Hydrophobically Modified Trypsin Inhibitors

NASA Astrophysics Data System (ADS)

Cubrilovic, Dragana; Biela, Adam; Sielaff, Frank; Steinmetzer, Torsten; Klebe, Gerhard; Zenobi, Renato

2012-10-01

NanoESI-MS is used for determining binding strengths of trypsin in complex with two different series of five congeneric inhibitors, whose binding affinity in solution depends on the size of the P3 substituent. The ligands of the first series contain a 4-amidinobenzylamide as P1 residue, and form a tight complex with trypsin. The inhibitors of the second series have a 2-aminomethyl-5-chloro-benzylamide as P1 group, and represent a model system for weak binders. The five different inhibitors of each group are based on the same scaffold and differ only in the length of the hydrophobic side chain of their P3 residue, which modulates the interactions in the S3/4 binding pocket of trypsin. The dissociation constants (KD) for high affinity ligands investigated by nanoESI-MS ranges from 15 nM to 450 nM and decreases with larger hydrophobic P3 side chains. Collision-induced dissociation (CID) experiments of five trypsin and benzamidine-based complexes show a correlation between trends in KD and gas-phase stability. For the second inhibitor series we could show that the effect of imidazole, a small stabilizing additive, can avoid the dissociation of the complex ions and as a result increases the relative abundance of weakly bound complexes. Here the KD values ranging from 2.9 to 17.6 μM, some 1-2 orders of magnitude lower than the first series. For both ligand series, the dissociation constants (KD) measured via nanoESI-MS were compared with kinetic inhibition constants (Ki) in solution.

Blackbody infrared radiative dissociation of oligonucleotide anions.

PubMed

Klassen, J S; Schnier, P D; Williams, E R

1998-11-01

The dissociation kinetics of a series of doubly deprotonated oligonucleotide 7-mers [d(A)7(2-), d(AATTAAT)2-, d(TTAATTA)2-, and d(CCGGCCG)2-] were measured using blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. The oligonucleotides dissociate first by cleavage at the glycosidic bond leading to the loss of a neutral nucleobase, followed by cleavage at the adjacent (5') phosphodiester bond to produce structurally informative a-base and w type ions. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained for the loss of base. The measured Arrhenius parameters are dependent on the identity of the nucleobase. The process involving the loss of an adenine base from the dianions, d(A)7(2-), d(AATTAAT)2-, and d(TTAATTA)2- has an average activation energy (Ea) of approximately 1.0 eV and a preexponential factor (A) of 10(10) s-1. Both guanine and cytosine base loss occurs for d(CCGGCCG)2-. The average Arrhenius parameters for the loss of cytosine and guanine are Ea = 1.32 +/- 0.03 eV and A = 10(13.3 +/- 0.3) s-1. No loss of thymine was observed for mixed adenine-thymine oligonucleotides. Neither base loss nor any other fragmentation reactions occur for d(T)7(2-) over a 600 s reaction delay at 207 degrees C, a temperature close to the upper limit accessible with our instrument. The Arrhenius parameters indicate that the preferred cleavage sites for mixed oligonucleotides of similar mass-to-charge ratio will be strongly dependent on the internal energy of the precursor ions. At low internal energies (effective temperatures below 475 K), loss of adenine and subsequent cleavage of the adjacent phosphoester bonds will dominate, whereas at higher energies, preferential cleavage at C and G residues will occur. The magnitude of the A factors < or = 10(13) s-1 measured for the loss of the three nucleobases (A, G, and C) is indicative of an entropically

Blackbody Infrared Radiative Dissociation of Oligonucleotide Anions

PubMed Central

Klassen, John S.; Schnier, Paul D.; Williams, Evan R.

2005-01-01

The dissociation kinetics of a series of doubly deprotonated oligonucleotide 7-mers [ d(A)72-, d(AATTAAT)2−, d(TTAATTA)2−, and d(CCGGCCG)2−] were measured using blackbody infrared radiative dissociation in a Fourier-transform mass spectrometer. The oligonucleotides dissociate first by cleavage at the glycosidic bond leading to the loss of a neutral nucleobase, followed by cleavage at the adjacent (5′) phosphodiester bond to produce structurally informative a-base and w type ions. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained for the loss of base. The measured Arrhenius parameters are dependent on the identity of the nucleobase. The process involving the loss of an adenine base from the dianions, d(A)72-, d(AATTAAT)2−, and d(TTAATTA)2− has an average activation energy (Ea) of ~1.0 eV and a preexponential factor (A) of 1010 s−1. Both guanine and cytosine base loss occurs for d(CCGGCCG)2−. The average Arrhenius parameters for the loss of cytosine and guanine are Ea = 1.32 ± 0.03 eV and A = 1013.3±0.3 s−1. No loss of thymine was observed for mixed adenine–thymine oligonucleotides. Neither base loss nor any other fragmentation reactions occur for d(T)72- over a 600 s reaction delay at 207 °C, a temperature close to the upper limit accessible with our instrument. The Arrhenius parameters indicate that the preferred cleavage sites for mixed oligonucleotides of similar mass-to-charge ratio will be strongly dependent on the internal energy of the precursor ions. At low internal energies (effective temperatures below 475 K), loss of adenine and subsequent cleavage of the adjacent phosphoester bonds will dominate, whereas at higher energies, preferential cleavage at C and G residues will occur. The magnitude of the A factors ≤1013 s−1 measured for the loss of the three nucleobases (A, G, and C) is indicative of an entropically neutral or

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

The Dissociative Subtype of Posttraumatic Stress Disorder (PTSD) Among Adolescents: Co-Occurring PTSD, Depersonalization/Derealization, and Other Dissociation Symptoms.

PubMed

Choi, Kristen R; Seng, Julia S; Briggs, Ernestine C; Munro-Kramer, Michelle L; Graham-Bermann, Sandra A; Lee, Robert C; Ford, Julian D

2017-12-01

The purpose of this study was to examine the co-occurrence of posttraumatic stress disorder (PTSD) and dissociation in a clinical sample of trauma-exposed adolescents by evaluating evidence for the depersonalization/derealization dissociative subtype of PTSD as defined by the DSM-5 and then examining a broader set of dissociation symptoms. A sample of treatment-seeking, trauma-exposed adolescents 12 to 16 years old (N = 3,081) from the National Child Traumatic Stress Network Core Data Set was used to meet the study objectives. Two models of PTSD/dissociation co-occurrence were estimated using latent class analysis, one with 2 dissociation symptoms and the other with 10 dissociation symptoms. After model selection, groups within each model were compared on demographics, trauma characteristics, and psychopathology. Model A, the depersonalization/derealization model, had 5 classes: dissociative subtype/high PTSD; high PTSD; anxious arousal; dysphoric arousal; and a low symptom/reference class. Model B, the expanded dissociation model, identified an additional class characterized by dissociative amnesia and detached arousal. These 2 models provide new information about the specific ways PTSD and dissociation co-occur and illuminate some differences between adult and adolescent trauma symptom expression. A dissociative subtype of PTSD can be distinguished from PTSD alone in adolescents, but assessing a wider range of dissociative symptoms is needed to fully characterize adolescent traumatic stress responses. Copyright © 2017 American Academy of Child and Adolescent Psychiatry. Published by Elsevier Inc. All rights reserved.

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.

Constants and thermodynamics of the acid-base equilibria of triglycine in water-ethanol solutions containing sodium perchlorate at 298 K

NASA Astrophysics Data System (ADS)

Pham Tkhi, L.; Usacheva, T. R.; Tukumova, N. V.; Koryshev, N. E.; Khrenova, T. M.; Sharnin, V. A.

2016-02-01

The acid-base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water-ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases p K 1) and increases the dissociation constant of the amino group of triglycine (decreases p K 2). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

Self-Injury and Suicide Attempt in Relation with Trauma and Dissociation among Adolescents with Dissociative and Non-Dissociative Disorders.

PubMed

Kılıç, Filiz; Coşkun, Murat; Bozkurt, Hasan; Kaya, İlyas; Zoroğlu, Salih

2017-03-01

To explore the role of trauma and dissociation over self-injurious behaviors (SIB) and suicide attempts (SA) in adolescents. A total of 207 adolescents participated in the study. After conducting diagnostic interview, participants were divided into five groups as subjects with dissociative disorders (DD), attention deficit hyperactivity disorder (ADHD), major depressive disorder (MDD) and anxiety disorders (AD), and a control group (CG) without any psychiatric disorder. ADHD, MDD and AD groups were considered as non-dissociative disorders (non-DD group) in the present study. There is no significant difference between groups in terms of number and age of the subjects (p>0.05). Among all participants SIB was reported in 32.2% of females (n=37) and 25% of males (n=23) while SA was reported in 29.6% of females (n=34) and 4.4% of males (n=4). Adolescents with DD were found to experience higher rates of SIB and SA than the other groups. Dissociation was the most important variable contributing to SIB and female gender was the most efficient variable for SA. Total trauma scores were also found to be significantly higher in DD group followed by non-DD and CG respectively. SIB and SA are complex behavioral problems which may be associated with many psychiatric factors. However higher level dissociation seems as an important mediating factor, even regardless of psychiatric diagnosis, in the development of SIB and SA. More research is needed to further explore the factors effective over SIB and SA in adolescents.

[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

A homogeneous, high-throughput-compatible, fluorescence intensity-based assay for UDP-N-acetylenolpyruvylglucosamine reductase (MurB) with nanomolar product detection.

PubMed

Shapiro, Adam B; Livchak, Stephania; Gao, Ning; Whiteaker, James; Thresher, Jason; Jahić, Haris; Huang, Jian; Gu, Rong-Fang

2012-03-01

A novel assay for the NADPH-dependent bacterial enzyme UDP-N-acetylenolpyruvylglucosamine reductase (MurB) is described that has nanomolar sensitivity for product formation and is suitable for high-throughput applications. MurB catalyzes an essential cytoplasmic step in the synthesis of peptidoglycan for the bacterial cell wall, reduction of UDP-N-acetylenolpyruvylglucosamine to UDP-N-acetylmuramic acid (UNAM). Interruption of this biosynthetic pathway leads to cell death, making MurB an attractive target for antibacterial drug discovery. In the new assay, the UNAM product of the MurB reaction is ligated to L-alanine by the next enzyme in the peptidoglycan biosynthesis pathway, MurC, resulting in hydrolysis of adenosine triphosphate (ATP) to adenosine diphosphate (ADP). The ADP is detected with nanomolar sensitivity by converting it to oligomeric RNA with polynucleotide phosphorylase and detecting the oligomeric RNA with a fluorescent dye. The product sensitivity of the new assay is 1000-fold greater than that of the standard assay that follows the absorbance decrease resulting from the conversion of NADPH to NADP(+). This sensitivity allows inhibitor screening to be performed at the low substrate concentrations needed to make the assay sensitive to competitive inhibition of MurB.

Dissociative Experiences and Vividness of Auditory Imagery

ERIC Educational Resources Information Center

Pérez-Fabello, María José; Campos, Alfredo

2017-01-01

The relationship between dissociation and auditory imagery were assessed, 2 variables that sometime influence on artistic creativity. A total of 170 fine arts undergraduates (94 women and 76 men) received 2 dissociation questionnaires--the Dissociative Ability Scale (DAS), and the Dissociative Experiences Scale (DES)--and 2 auditory imagery…

Reconsidering the autohypnotic model of the dissociative disorders.

PubMed

Dell, Paul F

2018-03-22

The dissociative disorders field and the hypnosis field currently reject the autohypnotic model of the dissociative disorders, largely because many correlational studies have shown hypnotizability and dissociation to be minimally related (r = .12). Curiously, it is also widely accepted that dissociative patients are highly hypnotizable. If dissociative patients are highly hypnotizable because only highly hypnotizable individuals can develop a dissociative disorder - as the author proposes - then the methodology of correlational studies of hypnotizability and dissociation in random clinical and community samples would necessarily be constitutively unable to detect, and statistically unable to reflect, that fact. That is, the autohypnotic, dissociative distancing of that small subset of highly hypnotizable individuals who repeatedly encountered intolerable circumstances is statistically lost among the data of (1) the highly hypnotizable subjects who do not dissociate and (2) subjects (of all levels of hypnotizability) who manifest other kinds of dissociation. The author proposes that, when highly hypnotizable individuals repeatedly engage in autohypnotic distancing from intolerable circumstances, they develop an overlearned, highly-motivated, automatized pattern of dissociative self-protection (i.e., a dissociative disorder). The author urges that theorists of hypnosis and the dissociative disorders explicitly include in their theories (a) the trait of high hypnotizability, (b) the phenomena of autohypnosis, and (c) the manifestations of systematized, autohypnotic pathology. Said differently, the author is suggesting that autohypnosis and autohypnotic pathology are unacknowledged nodes in the nomothetic networks of both hypnosis and dissociation.

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.

Dissociative tendencies and facilitated emotional processing.

PubMed

Oathes, Desmond J; Ray, William J

2008-10-01

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. (c) 2008 APA, all rights reserved

Dissociation in undergraduate students: disruptions in executive functioning.

PubMed

Giesbrecht, Timo; Merckelbach, Harald; Geraerts, Elke; Smeets, Ellen

2004-08-01

The concept of dissociation refers to disruptions in attentional control. Attentional control is an executive function. Few studies have addressed the link between dissociation and executive functioning. Our study investigated this relationship in a sample of undergraduate students (N = 185) who completed the Dissociative Experiences Scale and the Random Number Generation Task. We found that minor disruptions in executive functioning were related to a subclass of dissociative experiences, notably dissociative amnesia and the Dissociative Experiences Scale Taxon. However, the two other subscales of the Dissociative Experiences Scale, measuring depersonalization and absorption, were unrelated to executive functioning. Our findings suggest that a failure to inhibit previous responses might contribute to the pathological memory manifestations of dissociation.

[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.

Deuterium kinetic isotope effects on the dissociation of a protein-fatty acid complex in the gas phase.

PubMed

Liu, Lan; Michelsen, Klaus; Kitova, Elena N; Schnier, Paul D; Brown, Alex; Klassen, John S

2012-04-04

Deuterium kinetic isotope effects (KIEs) are reported for the first time for the dissociation of a protein-ligand complex in the gas phase. Temperature-dependent rate constants were measured for the loss of neutral ligand from the deprotonated ions of the 1:1 complex of bovine β-lactoglobulin (Lg) and palmitic acid (PA), (Lg + PA)(n-) → Lg(n-) + PA, at the 6- and 7- charge states. At 25 °C, partial or complete deuteration of the acyl chain of PA results in a measurable inverse KIE for both charge states. The magnitude of the KIEs is temperature dependent, and Arrhenius analysis of the rate constants reveals that deuteration of PA results in a decrease in activation energy. In contrast, there is no measurable deuterium KIE for the dissociation of the (Lg + PA) complex in aqueous solution at pH 8. Deuterium KIEs were calculated using conventional transition-state theory with an assumption of a late dissociative transition state (TS), in which the ligand is free of the binding pocket. The vibrational frequencies of deuterated and non-deuterated PA in the gas phase and in various solvents (n-hexane, 1-chlorohexane, acetone, and water) were established computationally. The KIEs calculated from the corresponding differences in zero-point energies account qualitatively for the observation of an inverse KIE but do not account for the magnitude of the KIEs nor their temperature dependence. It is proposed that the dissociation of the (Lg + PA) complex in aqueous solution also proceeds through a late TS in which the acyl chain is extensively hydrated such that there is no significant differential change in the vibrational frequencies along the reaction coordinate and, consequently, no significant KIE.

Dissociative Mothers' Subjective Experience of Parenting.

ERIC Educational Resources Information Center

Benjamin, Lynn R.; And Others

1996-01-01

A study of 54 mothers with a dissociative disorder, 20 mothers with other mental problems, and 20 normal mothers investigated what effect, if any, dissociation had on parenting. When tested on the Subjective Experiences of Parenting Scale, mothers with dissociation presented significantly more negative parenting behavior and attitudes. (CR)

Dissociative symptomatology in cancer patients.

PubMed

Civilotti, Cristina; Castelli, Lorys; Binaschi, Luca; Cussino, Martina; Tesio, Valentina; Di Fini, Giulia; Veglia, Fabio; Torta, Riccardo

2015-01-01

The utilization of the post-traumatic stress disorder (PTSD) diagnostic spectrum is currently being debated to categorize psychological adjustment in cancer patients. The aims of this study were to: (1) evaluate the presence of cancer-related traumatic dissociative symptomatology in a sample of cancer patients; (2) examine the correlation of cancer-related dissociation and sociodemographic and medical variables, anxiety, depression, and post-traumatic stress symptomatology; (3) investigate the predictors of cancer-related dissociation. Ninety-two mixed cancer patients (mean age: 58.94, ds = 10.13) recruited from two hospitals in northern Italy were administered a questionnaire on sociodemographic and medical characteristics, the Karnofsky Scale to measure the level of patient activity and medical care requirements, the Hospital Anxiety and Depression Scale (HADS) to evaluate the presence of anxiety and depression, the Impact of Event Scale Revised (IES-R) to assess the severity of intrusion, avoidance, and hypervigilance, and the Peritraumatic Dissociative Experiences Questionnaire (PDEQ) to quantify the traumatic dissociative symptomatology. 31.5% of participants report a PDEQ score above the cutoff. The results indicated that dissociative symptomatology was positively correlated with HADS scores (HADS-Anxiety: r = 0.476, p < 0.001; HADS-Depression: r = 0.364, p < 0.001) and with IES-R scores (IES-R-Intrusion: r = 0.698, p < 0.001; IES-R-Avoidance: r = 0.619, p < 0.001; IES-R- Hypervigilance: r = 0.681, p < 0.001). A stepwise regression analysis was performed in order to find the predictors of cancer-related traumatic dissociative symptomatology. The results converged on a three predictor model revealing that IES-R-Intrusion, IES-R-Avoidance, and IES-R-Hyperarousal accounted for 53.9% of the explained variance. These findings allow us to hypothesize a specific psychological reaction which may be ascribed to the traumatic spectrum within the context of cancer

Proton dissociation properties of arylphosphonates: Determination of accurate Hammett equation parameters.

PubMed

Dargó, Gergő; Bölcskei, Adrienn; Grün, Alajos; Béni, Szabolcs; Szántó, Zoltán; Lopata, Antal; Keglevich, György; Balogh, György T

2017-09-05

Determination of the proton dissociation constants of several arylphosphonic acid derivatives was carried out to investigate the accuracy of the Hammett equations available for this family of compounds. For the measurement of the pK a values modern, accurate methods, such as the differential potentiometric titration and NMR-pH titration were used. We found our results significantly different from the pK a values reported before (pK a1 : MAE = 0.16 pK a2 : MAE=0.59). Based on our recently measured pK a values, refined Hammett equations were determined that might be used for predicting highly accurate ionization constants of newly synthesized compounds (pK a1 =1.70-0.894σ, pK a2 =6.92-0.934σ). Copyright © 2017 Elsevier B.V. All rights reserved.

Empirical testing of criteria for dissociative schizophrenia.

PubMed

Laferrière-Simard, Marie-Christine; Lecomte, Tania; Ahoundova, Lola

2014-01-01

This study examined the validity of dissociative schizophrenia diagnostic criteria. In the first phase, 50 participants with a psychotic disorder were administered the Dissociative Experiences Scale and the Childhood Trauma Questionnaire to identify those with dissociative characteristics. In the second phase, we selected those who had a score of 15 or above on the Dissociative Experiences Scale. Fifteen of these participants were evaluated thoroughly with the Structured Clinical Interview for DSM-IV Axis I, Structured Clinical Interview for DSM-IV Axis II, and Structured Clinical Interview for DSM-IV Dissociative Disorders to determine whether they met the criteria for dissociative schizophrenia and to generate a clinical description. Our results indicated that 24% of the individuals we tested met these criteria. We propose making mandatory 1 of the 3 dissociative symptoms of the criteria to eliminate people with only nonspecific symptoms (e.g., extensive comorbidity). According to this modified criterion, 14% of our sample would receive a diagnosis of dissociative schizophrenia. However, a more comprehensive look at the clinical picture begs the question of whether dissociative schizophrenia is truly present in every person meeting the criteria. We discuss the relevance of creating a new schizophrenia subtype and offer recommendations for clinicians.

Comparing the symptoms and mechanisms of "dissociation" in dissociative identity disorder and borderline personality disorder.

PubMed

Laddis, Andreas; Dell, Paul F; Korzekwa, Marilyn

2017-01-01

A total of 75 patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised as having dissociative identity disorder (DID), and 100 patients were diagnosed with the Structured Interview for DSM-IV Personality as having borderline personality disorder (BPD). Both groups were administered the Multidimensional Inventory of Dissociation (MID). DID patients had significantly higher MID scores than BPD patients, different distributions of MID scores, and different MID subscale profiles in 3 ranges of MID scores (0-15, 15-30, 30-45). The core MID symptoms-exhibited at all ranges of MID scores-for DID patients (the presence of alters, identity confusion, and memory problems) and BPD patients (flashbacks, identity confusion, and memory problems) were ostensibly similar but were considered to be mostly produced by different underlying processes. Multiple regression analyses showed that the core MID symptoms of DID patients had different predictors than did the core MID symptoms of BPD patients. Alter identities seemed to generate most-but not all-dissociative phenomena in DID patients, whereas only the 24% highest scoring BPD patients (MID ≥45) seemed to manifest alter-driven dissociative experiences. Most BPD dissociative experiences appeared to be due to 5 other mechanisms: (a) BPD-specific, stress-driven, rapid shifts of self-state; (b and c) nondefensive disruptions of the framework of perceptual organization with or without an accompanying BPD-specific, dissociation-like disintegration of affective/neurocognitive functioning; (d) a defensive distancing or detachment from distress (i.e., simple depersonalization); and (e) Allen, Console, and Lewis's (1999) severe absorptive detachment.

[Dissociative phenomena in a sample of outpatients].

PubMed

Cantone, Daniela; Sperandeo, Raffaele; Maldonato, Mauro Nelson; Cozzolino, Pasquale; Perris, Francesco

2012-01-01

The study describes the frequency and the quality of dissociative phenomena and their relationship with axis I disorders and the psychopathological severity in outpatients. The sample (N=383) was subjected to MINI diagnostic interview and self-assessment scales DES and SCL-90. The data were analysed using SPSS. The 11,0% of subjects has a score ≥20 on DES. The 5,2% has no dissociative symptoms. The absorption images is the most frequent dissociative phenomenon, the less common is the dissociation amnesia. A relationship between dissociative phenomena and conditions unemployment, marital separation and single parties and an inverse relationship with age founded. Dissociative phenomena are more frequent in participants who have been diagnosed at least one axis I disorder and their severity is positively correlated with the number of diagnosed diseases and scores to the General Symptomatic Index. Our results point towards the existence of three types of dissociative experiences. The first type, represented by the factor absorption/imaginative involvement, is expressed along a continuum from normal to pathological; a second type, represented by the factor depersonalization/derealization, occurs in a significantly more intense and specific among subjects with axis I disorders; the latest manifestation dissociative, described by the dissociation amnesia, seems to have a predominantly typological feature that qualifies it as an experience not commonly distributed in the general population. The identifying of dissociative symptoms is necessary for the psychopathologic evaluation and to improve the effectiveness of treatment programs.

Calculation of the standard partial molal thermodynamic properties and dissociation constants of aqueous HCl{sup 0} and HBr{sup 0} at temperatures to 1000 C and pressures to 5 kbar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pokrovskii, V.A.

1999-04-01

Dissociation constants of aqueous ion pairs HCl{sup 0} and HBr{sup 0} derived in the literature from vapor pressure and supercritical conductance measurements (Quist and Marshall, 1968b; Frantz and Marshall, 1984) were used to calculate the standard partial molal thermodynamic properties of the species at 25 C and 1 bar. Regression of the data with the aid of revised Helgeson-Kirkham-Flowers equations of state (Helgeson et al., 1981; Tanger and Helgeson, 1988; Shock et al., 1989) resulted in a set of equations-of-state parameters that permits accurate calculation of the thermodynamic properties of the species at high temperatures and pressures. These properties andmore » parameters reproduce generally within 0.1 log unit (with observed maximum deviation of 0.23 log unit) the log K values for HBr{sup 0} and HCl{sup 0} given by Quist and Marshall (1968b) and Frantz and Marshall (1984), respectively, at temperatures to 800 C and pressures to 5 kbar.« less

Partition functions and equilibrium constants for diatomic molecules and atoms of astrophysical interest

NASA Astrophysics Data System (ADS)

Barklem, P. S.; Collet, R.

2016-04-01

Partition functions and dissociation equilibrium constants are presented for 291 diatomic molecules for temperatures in the range from near absolute zero to 10 000 K, thus providing data for many diatomic molecules of astrophysical interest at low temperature. The calculations are based on molecular spectroscopic data from the book of Huber & Herzberg (1979, Constants of Diatomic Molecules) with significant improvements from the literature, especially updated data for ground states of many of the most important molecules by Irikura (2007, J. Phys. Chem. Ref. Data, 36, 389). Dissociation energies are collated from compilations of experimental and theoretical values. Partition functions for 284 species of atoms for all elements from H to U are also presented based on data collected at NIST. The calculated data are expected to be useful for modelling a range of low density astrophysical environments, especially star-forming regions, protoplanetary disks, the interstellar medium, and planetary and cool stellar atmospheres. The input data, which will be made available electronically, also provides a possible foundation for future improvement by the community. Full Tables 1-8 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/588/A96

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. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Exposure to cadmium during in vitro maturation at environmental nanomolar levels impairs oocyte fertilization through oxidative damage: A large animal model study.

PubMed

Martino, N A; Marzano, G; Mangiacotti, M; Miedico, O; Sardanelli, A M; Gnoni, A; Lacalandra, G M; Chiaravalle, A E; Ciani, E; Bogliolo, L; Minervini, F; Pizzi, F; Dell'Aquila, M E

2017-04-01

Cadmium is a highly toxic heavy metal with negative effects on oocyte fertilization. The aim of this study was to analyse whether cadmium-induced impairment of fertilization is caused by mitochondria dysfunction and oxidative stress in the cumulus-oocyte complex (COC). Preliminarily, 19 trace element levels were measured in ovaries from juvenile and adult ewes and age-related cadmium ovarian bioaccumulation at nanomolar concentrations was found. COCs from juvenile and adult ewes, exposed during in vitro maturation to 1nM or 100nM CdCl 2 , and subjected to in vitro fertilization showed significantly lower fertilization rates in exposed COCs compared with controls. In vitro matured exposed and control COCs underwent confocal microscopy analysis of mitochondria activity and reactive oxygen species (ROS) levels and lipid peroxidation (LPO) assay at cumulus cell and oocyte level. In both age groups, cadmium at nanomolar concentrations induced cumulus-oocyte mitochondria over-activity and oxidative damage which were related to impaired oocyte fertilization. Copyright © 2017 Elsevier Inc. All rights reserved.

Evaluation of kinetic constants of biomolecular interaction on optical surface plasmon resonance sensor with Newton Iteration Method

NASA Astrophysics Data System (ADS)

Zhao, Yuanyuan; Jiang, Guoliang; Hu, Jiandong; Hu, Fengjiang; Wei, Jianguang; Shi, Liang

2010-10-01

In the immunology, there are two important types of biomolecular interaction: antigens-antibodies and receptors-ligands. Monitoring the response rate and affinity of biomolecular interaction can help analyze the protein function, drug discover, genomics and proteomics research. Moreover the association rate constant and dissociation rate constant of receptors-ligands are the important parameters for the study of signal transmission between cells. Recent advances in bioanalyzer instruments have greatly simplified the measurement of the kinetics of molecular interactions. Non-destructive and real-time monitoring the response to evaluate the parameters between antigens and antibodies can be performed by using optical surface plasmon resonance (SPR) biosensor technology. This technology provides a quantitative analysis that is carried out rapidly with label-free high-throughput detection using the binding curves of antigens-antibodies. Consequently, the kinetic parameters of interaction between antigens and antibodies can be obtained. This article presents a low cost integrated SPR-based bioanalyzer (HPSPR-6000) designed by ourselves. This bioanalyzer is mainly composed of a biosensor TSPR1K23, a touch-screen monitor, a microprocessor PIC24F128, a microflow cell with three channels, a clamp and a photoelectric conversion device. To obtain the kinetic parameters, sensorgrams may be modeled using one of several binding models provided with BIAevaluation software 3.0, SensiQ or Autolab. This allows calculation of the association rate constant (ka) and the dissociation rate constant (kd). The ratio of ka to kd can be used to estimate the equilibrium constant. Another kind is the analysis software OriginPro, which can process the obtained data by nonlinear fitting and then get some correlative parameters, but it can't be embedded into the bioanalyzer, so the bioanalyzer don't support the use of OriginPro. This paper proposes a novel method to evaluate the kinetic parameters

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.

The role of equilibrium and kinetic properties in the dissociation of Gd[DTPA-bis(methylamide)] (Omniscan) at near to physiological conditions.

PubMed

Baranyai, Zsolt; Brücher, Ernő; Uggeri, Fulvio; Maiocchi, Alessandro; Tóth, Imre; Andrási, Melinda; Gáspár, Attila; Zékány, László; Aime, Silvio

2015-03-16

[Gd(DTPA-BMA)] is the principal constituent of Omniscan, a magnetic resonance imaging (MRI) contrast agent. In body fluids, endogenous ions (Zn(2+), Cu(2+), and Ca(2+)) may displace the Gd(3+). To assess the extent of displacement at equilibrium, the stability constants of DTPA-BMA(3-) complexes of Gd(3+), Ca(2+), Zn(2+), and Cu(2+) have been determined at 37 °C in 0.15 M NaCl. The order of these stability constants is as follows: GdL≈CuL>ZnL≫CaL. Applying a simplified blood plasma model, the extent of dissociation of Omniscan (0.35 mM [Gd(DTPA-BMA)]) was found to be 17% by the formation of Gd(PO4), [Zn(DTPA-BMA)](-) (2.4%), [Cu(DTPA-BMA)](-) (0.2%), and [Ca(DTPA-BMA)](-) (17.7%). By capillary electrophoresis, the formation of [Ca(DTPA-BMA)](-) has been detected in human serum spiked with [Gd(DTPA-BMA)] (2.0 mM) at pH 7.4. Transmetallation reactions between [Gd(DTPA-BMA)] and Cu(2+) at 37 °C in the presence of citrate, phosphate, and bicarbonate ions occur by dissociation of the complex assisted by the endogenous ligands. At physiological concentrations of citrate, phosphate, and bicarbonate ions, the half-life of dissociation of [Gd(DTPA-BMA)] was calculated to be 9.3 h at pH 7.4. Considering the rates of distribution and dissociation of [Gd(DTPA-BMA)] in the extracellular space of the body, an open two-compartment model has been developed, which allows prediction of the extent of dissociation of the Gd(III) complex in body fluids depending on the rate of elimination of the contrast agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodamine B conjugates of triterpenoic acids are cytotoxic mitocans even at nanomolar concentrations.

PubMed

Sommerwerk, Sven; Heller, Lucie; Kerzig, Christoph; Kramell, Annemarie E; Csuk, René

2017-02-15

Triterpenoic acids 1-6 exhibited very low or no cytotoxicity at all, but their corresponding 2,3-di-O-acetyl-piperazinyl amides 13-18 showed low EC 50 values for several human tumor cell lines. Their cytotoxicity, however, was also high for the non-malignant mouse fibroblasts NIH 3T3. A significant improvement was achieved by preparing the rhodamine B derivatives 19-24. While rhodamine B is not cytotoxic (up to a concentration of 30μM - cut-off of the assay), the triterpenoid piperazine-spacered rhodamine B derivatives were cytotoxic in nano-molar concentration. Compound 24 (a diacetylated maslinic acid derivative) was most toxic for several human tumor cell lines but less toxic for mouse fibroblasts NIH 3T3. Staining and double-staining experiments revealed 24 to act as a mitocan. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Theoretical and Experimental Investigation of Heat Conduction in Air, Including Effects of Oxygen Dissociation

NASA Technical Reports Server (NTRS)

Hansen, C. Frederick; Early, Richard A.; Alzofon, Frederick E.; Witteborn, Fred C.

1959-01-01

Solutions are presented for the conduction of beat through a semi-infinite gas medium having a uniform initial temperature and a constant boundary temperature. The coefficients of thermal conductivity and diffusivity are treated as variables, and the solutions are extended to the case of air at temperatures where oxygen dissociation occurs. These solutions are used together with shock-tube measurements to evaluate the integral of thermal conductivity for air as a function of temperature.

Simple dissociations for a higher-powered neuropsychology.

PubMed

McIntosh, Robert D

2018-06-01

Dissociations in cognitive neuropsychology are often investigated at the level of the single-case, and formal criteria exist for the detection of dissociations, and their sub-classification into 'classical' and 'strong' types. These criteria require a patient to show a frank deficit on one task (for a classical dissociation) or both tasks (for a strong dissociation), and a significantly extreme difference between tasks. I propose that only the significant between-task difference is logically necessary, and that if this simple criterion is met, the patient should be said to show a dissociation. Using Monte Carlo simulations, I show that this simplification increases the power to detect dissociations across a range of practically-relevant conditions, whilst retaining excellent control over Type I error. Additional testing for frank deficits on each task provides further qualifying information, but using these test outcomes to categorise dissociations as classical or strong may be too uncertain to guide theoretical inferences reliably. I suggest that we might instead characterise the strength of the dissociation using a continuous index, such as the effect size of the between-task difference. Copyright © 2018 Elsevier Ltd. All rights reserved.

On the dissociation and conformation of gas-phase methonium ions.

PubMed

Gross, Deborah S; Williams, Evan R

1996-12-20

The dissociation pathways of both doubly and singly charged methonium ions, (CH(3))(3)N(+) -(CH(2))(n)-(+)N(CH(3))(3)·X(-) (n = 6,10; X = Br, I, and OAc), are measured using blackbody infrared radiative dissociation (BIRD) and SORI-CAD in a Fourier transform mass spectrometer. SORI-CAD of the doubly charged decamethonium ions results primarily in the formation of even electron ions by hydrogen rearrangements. In contrast, homolytic bond cleavage to form two odd electron ions is highly favored in the hexamethonium ion, presumably due to increased Coulomb repulsion in this ion. For BIRD of the singly charged salts, ions are mass selected and dissociated by heating the vacuum chamber to elevated temperatures. Under the low pressure conditions of our experiment, energy is transferred from the chamber walls to the ions by the absorption of blackbody radiation. From the temperature dependence of the unimolecular rate constants for dissociation, Arrhenius activation energies in the zero-pressure limit are obtained. The primary dissociation pathways correspond to counterion substitution reactions which result in loss of N(CH(3))(3) and CH(3)X. For hexamethonium and decamethonium with X = Br or I, the branching ratios for these pathways differ dramatically; the ratio of loss of N(CH(3))(3) and CH(3)Br is 3.8 and 0.4 for hexamethonium and decamethonium bromide, respectively. The hexamethonium acetate salt has a branching ratio of 0.1. The Arrhenius activation energies for hexamethonium (Br or I) and decamethonium (Br or I) are 0.9 and 1.0 eV, respectively. This value for hexamethonium acetate is 0.6 eV. Molecular dynamics simulations and Monte Carlo conformation searching are used to obtain the lowest energy structures of hexamethonium and decamethonium bromide. These calculations indicate that the methonium ion folds around the counterion to form a cyclic salt-bridge structure in which both quaternary nitrogens interact with the oppositely charged counterion. The

On the dissociation and conformation of gas-phase methonium ions

PubMed Central

Gross, Deborah S.

2005-01-01

The dissociation pathways of both doubly and singly charged methonium ions, (CH3)3N+ –(CH2)n–+N(CH3)3·X− (n = 6,10; X = Br, I, and OAc), are measured using blackbody infrared radiative dissociation (BIRD) and SORI–CAD in a Fourier transform mass spectrometer. SORI–CAD of the doubly charged decamethonium ions results primarily in the formation of even electron ions by hydrogen rearrangements. In contrast, homolytic bond cleavage to form two odd electron ions is highly favored in the hexamethonium ion, presumably due to increased Coulomb repulsion in this ion. For BIRD of the singly charged salts, ions are mass selected and dissociated by heating the vacuum chamber to elevated temperatures. Under the low pressure conditions of our experiment, energy is transferred from the chamber walls to the ions by the absorption of blackbody radiation. From the temperature dependence of the unimolecular rate constants for dissociation, Arrhenius activation energies in the zero-pressure limit are obtained. The primary dissociation pathways correspond to counterion substitution reactions which result in loss of N(CH3)3 and CH3X. For hexamethonium and decamethonium with X = Br or I, the branching ratios for these pathways differ dramatically; the ratio of loss of N(CH3)3 and CH3Br is 3.8 and 0.4 for hexamethonium and decamethonium bromide, respectively. The hexamethonium acetate salt has a branching ratio of 0.1. The Arrhenius activation energies for hexamethonium (Br or I) and decamethonium (Br or I) are 0.9 and 1.0 eV, respectively. This value for hexamethonium acetate is 0.6 eV. Molecular dynamics simulations and Monte Carlo conformation searching are used to obtain the lowest energy structures of hexamethonium and decamethonium bromide. These calculations indicate that the methonium ion folds around the counterion to form a cyclic salt-bridge structure in which both quaternary nitrogens interact with the oppositely charged counterion. The significantly different

Nanomolar pyrophosphate detection and nucleus staining in living cells with simple terpyridine-Zn(II) complexes.

PubMed

Chao, Duobin; Ni, Shitan

2016-05-20

Great efforts have been made to develop fluorescent probes for pyrophosphate (PPi) detection. Nucleus staining with fluorescence microscopy has been also widely investigated. But fluorescent probes for PPi detection with high sensitivity in water medium and nucleus staining with low-cost non-precious metal complexes in living cells are still challenging. Herein, we report simple terpyridine-Zn(II) complexes for selective nanomolar PPi detection over ATP and ADP in water based on aggregation induced emission (AIE) and intramolecular charge transfer (ICT). In addition, these terpyridine-Zn(II) complexes were successfully employed for nucleus staining in living cells. These results demonstrated simply obtained terpyridine-Zn(II) complexes are powerful tool for PPi detection and the development of PPi-related studies.

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(+).

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

Open scapulothoracic dissociation.

PubMed

Fischer, P J; Kent, R B

2001-04-01

Scapulothoracic dissociation refers to the traumatic separation of the shoulder from the chest wall. This most commonly occurs as a closed injury. We present a case of open scapulothoracic dissociation and emphasize clinical features unique to this injury. In both closed and open scapulothoracic dissociation, the force necessary to shear the scapula from its thoracic attachments results in vascular disruption and neurologic injury to the upper extremity. As a consequence, patients have a pulseless, flail upper extremity with a significant chest wall hematoma (closed) or active bleeding (open). The first priority is to resuscitate and address life-threatening injuries. If the patient has active bleeding, immediate vascular control to prevent exsanguination is essential. Patients with ischemia and an incomplete injury or unreliable neurologic examination need revascularization. Outcome is based on the extent of brachial plexus or cervical nerve root avulsion. Patients with loss of neurologic function ultimately benefit from amputation at the appropriate level.

Dissociative disorders and dissociative symptoms among veterans of the Iraq-Iran war suffering from chronic post-traumatic disorder.

PubMed

Nejad, Alireza G; Farahati, Hamid

2007-10-01

To evaluate any dissociative disorders in patients with post traumatic stress disorder (PTSD), and find any relationship between dissociation and related variables in these patients. A case controlled study carried out among 130 male patients with PTSD, and 130 matched individuals from the normal population. The study was carried out between January and September 2005, at Beheshti Psychiatric Hospital, Kerman, Iran, Demographic data and history of childhood physical abuse and self-harm in both groups were recorded. The severity of PTSD was measured by Davidson PTSD scale in the study group. Dissociative symptoms were evaluated with the dissociative experience scale (DES). For evaluating dissociative disorders, the dissociative disorder interview schedule (DDIS) was used. Data were analyzed by SPSS software. The mean age (+/- SD) of veterans was 41.46 (+/-5.09) years, and the mean age of going to the combat area was 29.4 (+/-5.015). The mean duration of involvement in combat was 27.8 (+/-23.44) months. The mean DES score in the study group was 26.01 (+/-12.31) and was 9.58 (+/-7.23) in the control group (F=1.171, p<0.0001). The mean score (+/-SD) of Davidson PTSD scale was 54+/-96 in the study group. The most prevalent dissociative disorder in the study group was psychogenic amnesia. Many veterans with the impression of chronic PTSD may have an additional diagnosis of dissociative disorders.

Dissociative Disorders Among Chinese Inpatients Diagnosed With Schizophrenia

PubMed Central

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 the study was to assess the prevalence of dissociative disorders in a sample of Chinese psychiatric inpatients. Participants in the study consisted of 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 for Mental Disorders, Version 3 (CCMD-3). All participants completed a self-report measure of dissociation, the Dissociative Experiences Scale (DES) and none had a prior diagnosis of a dissociative disorder. Ninety-six randomly selected participants were interviewed with a structured interview, the Dissociative Disorders Interview Schedule (DDIS) and a clinical interview. These 96 patients did not differ significantly from the 473 patients who were not interviewed on any demographic measures or on the self-report measure dissociation. A total of 28 (15.3%, after weighting of the data) patients received a clinical diagnosis of a dissociative disorder based on DSM-IV-TR criteria. Dissociative identity disorder was diagnosed in 2 (0.53%, after weighting) patients. Compared to the patients without a dissociative disorder, patients with dissociative disorders were significantly more likely to report childhood abuse (57.1% versus 22.1%), but the two groups did not differ significantly on any demographic measures. Dissociative disorders were readily identified in an inpatient psychiatric population in China. PMID:20603768

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.

Crystal-defect-induced facet-dependent electrocatalytic activity of 3D gold nanoflowers for the selective nanomolar detection of ascorbic acid.

PubMed

De, Sandip Kumar; Mondal, Subrata; Sen, Pintu; Pal, Uttam; Pathak, Biswarup; Rawat, Kuber Singh; Bardhan, Munmun; Bhattacharya, Maireyee; Satpati, Biswarup; De, Amitabha; Senapati, Dulal

2018-06-14

Understanding and exploring the decisive factors responsible for superlative catalytic efficiency is necessary to formulate active electrode materials for improved electrocatalysis and high-throughput sensing. This research demonstrates the ability of bud-shaped gold nanoflowers (AuNFs), intermediates in the bud-to-blossom gold nanoflower synthesis, to offer remarkable electrocatalytic efficiency in the oxidation of ascorbic acid (AA) at nanomolar concentrations. Multicomponent sensing in a single potential sweep is measured using differential pulse voltammetry while the kinetic parameters are estimated using electrochemical impedance spectroscopy. The outstanding catalytic activity of bud-structured AuNF [iAuNFp(Bud)/iGCp ≅ 100] compared with other bud-to-blossom intermediate nanostructures is explained by studying their structural transitions, charge distributions, crystalline patterns, and intrinsic irregularities/defects. Detailed microscopic analysis shows that density of crystal defects, such as edges, terraces, steps, ledges, kinks, and dislocation, plays a major role in producing the high catalytic efficiency. An associated ab initio simulation provides necessary support for the projected role of different crystal facets as selective catalytic sites. Density functional theory corroborates the appearance of inter- and intra-molecular hydrogen bonding within AA molecules to control the resultant fingerprint peak potentials at variable concentrations. Bud-structured AuNF facilitates AA detection at nanomolar levels in a multicomponent pathological sample.

Dancing with the Muses: dissociation and flow.

PubMed

Thomson, Paula; Jaque, S Victoria

2012-01-01

This study investigated dissociative psychological processes and flow (dispositional and state) in a group of professional and pre-professional dancers (n=74). In this study, high scores for global (Mdn=4.14) and autotelic (Mdn=4.50) flow suggest that dancing was inherently integrating and rewarding, although 17.6% of the dancers were identified as possibly having clinical levels of dissociation (Dissociative Experiences Scale-Taxon cutoff score≥20). The results of the multivariate analysis of variance indicated that subjects with high levels of dissociation had significantly lower levels of global flow (p<.05). Stepwise linear regression analyses demonstrated that dispositional flow negatively predicted the dissociative constructs of depersonalization and taxon (p<.05) but did not significantly predict the variance in absorption/imagination (p>.05). As hypothesized, dissociation and flow seem to operate as different mental processes.

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.

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.

Calculation of the rate constant for state-selected recombination of H+O2(v) as a function of temperature and pressure

NASA Astrophysics Data System (ADS)

Teitelbaum, Heshel; Caridade, Pedro J. S. B.; Varandas, António J. C.

2004-06-01

Classical trajectory calculations using the MERCURY/VENUS code have been carried out on the H+O2 reactive system using the DMBE-IV potential energy surface. The vibrational quantum number and the temperature were selected over the ranges v=0 to 15, and T=300 to 10 000 K, respectively. All other variables were averaged. Rate constants were determined for the energy transfer process, H+O2(v)-->H+O2(v''), for the bimolecular exchange process, H+O2(v)-->OH(v')+O, and for the dissociative process, H+O2(v)-->H+O+O. The dissociative process appears to be a mere extension of the process of transferring large amounts of energy. State-to-state rate constants are given for the exchange reaction, and they are in reasonable agreement with previous results, while the energy transfer and dissociative rate constants have never been reported previously. The lifetime distributions of the HO2 complex, calculated as a function of v and temperature, were used as a basis for determining the relative contributions of various vibrational states of O2 to the thermal rate coefficients for recombination at various pressures. This novel approach, based on the complex's ability to survive until it collides in a secondary process with an inert gas, is used here for the first time. Complete falloff curves for the recombination of H+O2 are also calculated over a wide range of temperatures and pressures. The combination of the two separate studies results in pressure- and temperature-dependent rate constants for H+O2(v)(+Ar)⇄HO2(+Ar). It is found that, unlike the exchange reaction, vibrational and rotational-translational energy are liabilities in promoting recombination.

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Xia; Johs, Alexander; Zhao, Linduo

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less

Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

DOE PAGES

Lu, Xia; Johs, Alexander; Zhao, Linduo; ...

2018-05-29

Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less

Dissociation rate of bromine diatomics in an argon heat bath

NASA Technical Reports Server (NTRS)

Razner, R.; Hopkins, D.

1973-01-01

The evolution of a collection of 300 K bromine diatomics embedded in a heat bath of argon atoms at 1800 K was studied by computer, and a dissociation-rate constant for the reaction Br2 + BR + Ar yields Br + Ar was determined. Previously published probability distributions for energy and angular momentum transfers in classical three-dimensional Br2-Ar collisions were used in conjunction with a newly developed Monte Carlo scheme for this purpose. Results are compared with experimental shock-tube data and the predictions of several other theoretical models. A departure from equilibrium is obtained which is significantly greater than that predicted by any of these other theories.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dissociation: Defining the Concept in Criminal Forensic Psychiatry.

PubMed

Bourget, Dominique; Gagné, Pierre; Wood, Stephen Floyd

2017-06-01

Claims of amnesia and dissociative experiences in association with a violent crime are not uncommon. Research has shown that dissociation is a risk factor for violence and is seen most often in crimes of extreme violence. The subject matter is most relevant to forensic psychiatry. Peritraumatic dissociation for instance, with or without a history of dissociative disorder, is quite frequently reported by offenders presenting for a forensic psychiatric examination. Dissociation or dissociative amnesia for serious offenses can have legal repercussions stemming from their relevance to the legal constructs of fitness to stand trial, criminal responsibility, and diminished capacity. The complexity in forensic psychiatric assessments often lies in the difficulty of connecting clinical symptomatology reported by violent offenders to a specific condition included in the Diagnostic and Statistical Manual of Mental Disorders (DSM). This article provides a review of diagnostic considerations with regard to dissociation across the DSM nomenclature, with a focus on the main clinical constructs related to dissociation. Forensic implications are discussed, along with some guides for the forensic evaluator of offenders presenting with dissociation. © 2017 American Academy of Psychiatry and the Law.

Dissociation Energies of the Alkaline Earth Monofluorides

DOE Office of Scientific and Technical Information (OSTI.GOV)

BLUE, GARY D.; GREEN, JOHN W.; EHLERT, THOMAS C.

1963-08-24

New results and theoretical calculations are presented that indicate consistently high dissocintion energies for all the alkaline earth monofluorides. Experimental results were obtained by utilizing a mass spectrometer to analyze the vapors from a heated Ta Knudsen cell containing an alkaline earth fluoride salt with Al present as a reducing agent. Ionization efficiency curves were obtained and temperature dependence investigations were made to determine the molecular precursor of the ions observed. Values of the equilibrium constants at different temperatures were used together with the free-energy functions to calculate the third law heats of reaction at 298 deg K. Data aremore » tabulated for the heats of various reactions for Al--MF2 systems with M = Mg, Ca, Sr, and Ba, and dissociation energies of MF molecules by various methods for Be, Mg, Ca, Sr, and Ba. (C.H.)« less

Intimate Partner Violence Among Patients With Dissociative Disorders.

PubMed

Webermann, Aliya R; Brand, Bethany L; Kumar, Shaina A

2017-12-01

Childhood trauma is common among survivors and perpetrators of intimate partner violence (IPV). Although symptoms of posttraumatic stress disorder (PTSD) and dissociative disorders (DDs) are predictors of IPV victimization and perpetration, few studies explore IPV among those with DDs. The present study examined IPV and symptoms as predictors among participants in the Treatment of Patients With Dissociative Disorders (TOP DD) Network study, an educational intervention for individuals with DDs and their clinicians. Both clinicians and patients reported on patients' history of physical, emotional, and sexual IPV as both victims and perpetrators. Patients self-reported dissociative, posttraumatic (PTSD), and emotion dysregulation symptoms, as well as IPV-specific dissociative symptoms. According to patients and clinicians, patients were frequently victims of IPV, most commonly emotional IPV. Dissociative symptoms predicted IPV exposure, whereas dissociative and emotion dysregulation symptoms predicted IPV-specific dissociative symptoms.

Dissociation of I II in chemical oxygen-iodine lasers: experiment, modeling, and pre-dissociation by electrical discharge

NASA Astrophysics Data System (ADS)

Katz, A.; Waichman, K.; Dahan, Z.; Rybalkin, V.; Barmashenko, B. D.; Rosenwaks, S.

2007-06-01

The dissociation of I II molecules at the optical axis of a supersonic chemical oxygen-iodine laser (COIL) was studied via detailed measurements and three dimensional computational fluid dynamics calculations. Comparing the measurements and the calculations enabled critical examination of previously proposed dissociation mechanisms and suggestion of a mechanism consistent with the experimental and theoretical results obtained in a supersonic COIL for the gain, temperature and I II dissociation fraction at the optical axis. The suggested mechanism combines the recent scheme of Azyazov and Heaven (AIAA J. 44, 1593 (2006)), where I II(A' 3Π 2u), I II(A 3Π 1u) and O II(a1Δ g, v) are significant dissociation intermediates, with the "standard" chain branching mechanism of Heidner et al. (J. Phys. Chem. 87, 2348 (1983)), involving I(2P 1/2) and I II(X1Σ + g, v). In addition, we examined a new method for enhancement of the gain and power in a COIL by applying DC corona/glow discharge in the transonic section of the secondary flow in the supersonic nozzle, dissociating I II prior to its mixing with O II(1Δ). The loss of O II(1Δ) consumed for dissociation was thus reduced and the consequent dissociation rate downstream of the discharge increased, resulting in up to 80% power enhancement. The implication of this method for COILs operating beyond the specific conditions reported here is assessed.

Fatty acids bind tightly to the N-terminal domain of angiopoietin-like protein 4 and modulate its interaction with lipoprotein lipase.

PubMed

Robal, Terje; Larsson, Mikael; Martin, Miina; Olivecrona, Gunilla; Lookene, Aivar

2012-08-24

Angiopoietin-like protein 4 (Angptl4), a potent regulator of plasma triglyceride metabolism, binds to lipoprotein lipase (LPL) through its N-terminal coiled-coil domain (ccd-Angptl4) inducing dissociation of the dimeric enzyme to inactive monomers. In this study, we demonstrate that fatty acids reduce the inactivation of LPL by Angptl4. This was the case both with ccd-Angptl4 and full-length Angptl4, and the effect was seen in human plasma or in the presence of albumin. The effect decreased in the sequence oleic acid > palmitic acid > myristic acid > linoleic acid > linolenic acid. Surface plasmon resonance, isothermal titration calorimetry, fluorescence, and chromatography measurements revealed that fatty acids bind with high affinity to ccd-Angptl4. The interactions were characterized by fast association and slow dissociation rates, indicating formation of stable complexes. The highest affinity for ccd-Angptl4 was detected for oleic acid with a subnanomolar equilibrium dissociation constant (K(d)). The K(d) values for palmitic and myristic acid were in the nanomolar range. Linoleic and linolenic acid bound with much lower affinity. On binding of fatty acids, ccd-Angptl4 underwent conformational changes resulting in a decreased helical content, weakened structural stability, dissociation of oligomers, and altered fluorescence properties of the Trp-38 residue that is located close to the putative LPL-binding region. Based on these results, we propose that fatty acids play an important role in modulating the effects of Angptl4.

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…

Binding Energies of Proton-Bound Dimers of Imidazole and n-Acetylalanine Methyl Ester Obtained by Blackbody Infrared Radiative Dissociation

PubMed Central

Jockusch, Rebecca A.; Williams*, Evan R.

2005-01-01

The dissociation kinetics of protonated n-acetyl-L-alanine methyl ester dimer (AcAlaMEd), imidazole dimer, and their cross dimer were measured using blackbody infrared radiative dissociation (BIRD). Master equation modeling of these data was used to extract threshold dissociation energies (Eo) for the dimers. Values of 1.18 ± 0.06, 1.11 ± 0.04, and 1.12 ± 0.08 eV were obtained for AcAlaMEd, imidazole dimer, and the cross dimer, respectively. Assuming that the reverse activation barrier for dissociation of the ion–molecule complex is negligible, the value of Eo can be compared to the dissociation enthalpy (ΔHd°) from HPMS data. The Eo values obtained for the imidazole dimer and the cross dimer are in agreement with HPMS values; the value for AcAlaMEd is somewhat lower. Radiative rate constants used in the master equation modeling were determined using transition dipole moments calculated at the semiempirical (AM1) level for all dimers and compared to ab initio (RHF/3-21G*) calculations where possible. To reproduce the experimentally measured dissociation rates using master equation modeling, it was necessary to multiply semiempirical transition dipole moments by a factor between 2 and 3. Values for transition dipole moments from the ab initio calculations could be used for two of the dimers but appear to be too low for AcAlaMEd. These results demonstrate that BIRD, in combination with master equation modeling, can be used to determine threshold dissociation energies for intermediate size ions that are in neither the truncated Boltzmann nor the rapid energy exchange limit. PMID:16604163

UV-Vis spectrophotometric studies of self-oxidation/dissociation of quaternary ammonium permanganates (QAP) - impact of solvent polarity

NASA Astrophysics Data System (ADS)

Bank, Suraj Prakash; Guru, Partha Sarathi; Dash, Sukalyan

2015-05-01

Self-oxidation/dissociation of some quaternary ammonium permanganates (QAPs), such as cetyltrimethylammonium permanganate (CTAP) and tetrabutylammonium permanganate (TBAP), have been studied spectrophotometrically in six different organic solvent media of different polarities wherein the compounds show good solubility and stability. The optical densities of the substrates at zero time (ODo) and first-order rate constants of dissociation (k1) have been determined from their successive scanning for 40 min. At comparable experimental conditions, absorption capabilities of the substrates are compared from the ODo values in various organic media; the stability of the solutions is compared from the successive scan spectra in those media. The ODo values and the k1 values have been plotted against some solvent parameters to understand their effects on the absorbance and reactivity of the QAPs. These data are also subjected to multiple regression analysis to explain the influence of various solvent parameters on the ion-pairing properties of the substrates, thus elucidating their effects on the process of self-oxidation/dissociation of the substrates.

Molecular modeling of the dissociation of methane hydrate in contact with a silica surface.

PubMed

Bagherzadeh, S Alireza; Englezos, Peter; Alavi, Saman; Ripmeester, John A

2012-03-15

We use constant energy, constant volume (NVE) molecular dynamics simulations to study the dissociation of the fully occupied structure I methane hydrate in a confined geometry between two hydroxylated silica surfaces between 36 and 41 Å apart, at initial temperatures of 283, 293, and 303 K. Simulations of the two-phase hydrate/water system are performed in the presence of silica, with and without a 3 Å thick buffering water layer between the hydrate phase and silica surfaces. Faster decomposition is observed in the presence of silica, where the hydrate phase is prone to decomposition from four surfaces, as compared to only two sides in the case of the hydrate/water simulations. The existence of the water layer between the hydrate phase and the silica surface stabilizes the hydrate phase relative to the case where the hydrate is in direct contact with silica. Hydrates bound between the silica surfaces dissociate layer-by-layer in a shrinking core manner with a curved decomposition front which extends over a 5-8 Å thickness. Labeling water molecules shows that there is exchange of water molecules between the surrounding liquid and intact cages in the methane hydrate phase. In all cases, decomposition of the methane hydrate phase led to the formation of methane nanobubbles in the liquid water phase. © 2012 American Chemical Society

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…

Modulation of extrasynaptic NMDA receptors by synaptic and tonic zinc.

PubMed

Anderson, Charles T; Radford, Robert J; Zastrow, Melissa L; Zhang, Daniel Y; Apfel, Ulf-Peter; Lippard, Stephen J; Tzounopoulos, Thanos

2015-05-19

Many excitatory synapses contain high levels of mobile zinc within glutamatergic vesicles. Although synaptic zinc and glutamate are coreleased, it is controversial whether zinc diffuses away from the release site or whether it remains bound to presynaptic membranes or proteins after its release. To study zinc transmission and quantify zinc levels, we required a high-affinity rapid zinc chelator as well as an extracellular ratiometric fluorescent zinc sensor. We demonstrate that tricine, considered a preferred chelator for studying the role of synaptic zinc, is unable to efficiently prevent zinc from binding low-nanomolar zinc-binding sites, such as the high-affinity zinc-binding site found in NMDA receptors (NMDARs). Here, we used ZX1, which has a 1 nM zinc dissociation constant and second-order rate constant for binding zinc that is 200-fold higher than those for tricine and CaEDTA. We find that synaptic zinc is phasically released during action potentials. In response to short trains of presynaptic stimulation, synaptic zinc diffuses beyond the synaptic cleft where it inhibits extrasynaptic NMDARs. During higher rates of presynaptic stimulation, released glutamate activates additional extrasynaptic NMDARs that are not reached by synaptically released zinc, but which are inhibited by ambient, tonic levels of nonsynaptic zinc. By performing a ratiometric evaluation of extracellular zinc levels in the dorsal cochlear nucleus, we determined the tonic zinc levels to be low nanomolar. These results demonstrate a physiological role for endogenous synaptic as well as tonic zinc in inhibiting extrasynaptic NMDARs and thereby fine tuning neuronal excitability and signaling.

Modulation of extrasynaptic NMDA receptors by synaptic and tonic zinc

PubMed Central

Anderson, Charles T.; Radford, Robert J.; Zastrow, Melissa L.; Zhang, Daniel Y.; Apfel, Ulf-Peter; Lippard, Stephen J.; Tzounopoulos, Thanos

2015-01-01

Many excitatory synapses contain high levels of mobile zinc within glutamatergic vesicles. Although synaptic zinc and glutamate are coreleased, it is controversial whether zinc diffuses away from the release site or whether it remains bound to presynaptic membranes or proteins after its release. To study zinc transmission and quantify zinc levels, we required a high-affinity rapid zinc chelator as well as an extracellular ratiometric fluorescent zinc sensor. We demonstrate that tricine, considered a preferred chelator for studying the role of synaptic zinc, is unable to efficiently prevent zinc from binding low-nanomolar zinc-binding sites, such as the high-affinity zinc-binding site found in NMDA receptors (NMDARs). Here, we used ZX1, which has a 1 nM zinc dissociation constant and second-order rate constant for binding zinc that is 200-fold higher than those for tricine and CaEDTA. We find that synaptic zinc is phasically released during action potentials. In response to short trains of presynaptic stimulation, synaptic zinc diffuses beyond the synaptic cleft where it inhibits extrasynaptic NMDARs. During higher rates of presynaptic stimulation, released glutamate activates additional extrasynaptic NMDARs that are not reached by synaptically released zinc, but which are inhibited by ambient, tonic levels of nonsynaptic zinc. By performing a ratiometric evaluation of extracellular zinc levels in the dorsal cochlear nucleus, we determined the tonic zinc levels to be low nanomolar. These results demonstrate a physiological role for endogenous synaptic as well as tonic zinc in inhibiting extrasynaptic NMDARs and thereby fine tuning neuronal excitability and signaling. PMID:25947151

Recent developments in the theory of dissociation

PubMed Central

SPITZER, CARSTEN; BARNOW, SVEN; FREYBERGER, HARALD J; GRABE, HANS JOERGEN

2006-01-01

Although the construct of dissociation was introduced into psychiatry at the end of the 19th century by Pierre Janet, the term still lacks a coherent conceptualization, which is partially reflected by differences in the classification of dissociative and conversion disorders in ICD-10 and DSM-IV. Given the clinical significance of dissociative psychopathology in numerous clinical conditions, it is very valuable that various efforts have been made to refine and to specify current conceptualizations in recent years. The most promising and convincing approaches converge in subdividing dissociation into qualitatively different types, i.e. pathological versus non-pathological dissociation, and "detachment" versus "compartmentalization". We review these concepts and discuss their scientific and clinical potential as well as their limitations. PMID:16946940

Symptom overreporting and dissociative experiences: A qualitative review.

PubMed

Merckelbach, H; Boskovic, I; Pesy, D; Dalsklev, M; Lynn, S J

2017-03-01

We discuss a phenomenon that has received little attention to date in research on dissociative phenomena, namely that self-reports of these phenomena overlap with the tendency to overendorse eccentric items. We review the literature documenting the dissociation-overreporting link and then briefly discuss various interpretations of this link: (1) overreporting is an artifact of measuring dissociative symptoms; (2) dissociative psychopathology engenders overreporting of eccentric symptoms through fantasy proneness or impairments in internal monitoring; (3) an overreporting response style as is evident in malingerers, for example, promotes reports of dissociative symptoms. These three interpretations are not mutually exclusive. Also, the dissociation-overreporting link may have different origins among different samples. Because overreporting may introduce noise in datasets, we need more research specifically aimed at disentangling the dissociation-overreporting link. We suggest various avenues to accomplish this goal. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Nanomolar nitric oxide concentrations quickly and reversibly modulate astrocytic energy metabolism

PubMed Central

San Martín, Alejandro; Arce-Molina, Robinson; Galaz, Alex; Pérez-Guerra, Gustavo; Barros, L. Felipe

2017-01-01

Nitric oxide (NO) is an intercellular messenger involved in multiple bodily functions. Prolonged NO exposure irreversibly inhibits respiration by covalent modification of mitochondrial cytochrome oxidase, a phenomenon of pathological relevance. However, the speed and potency of NO's metabolic effects at physiological concentrations are incompletely characterized. To this end, we set out to investigate the metabolic effects of NO in cultured astrocytes from mice by taking advantage of the high spatiotemporal resolution afforded by genetically encoded Förster resonance energy transfer (FRET) nanosensors. NO exposure resulted in immediate and reversible intracellular glucose depletion and lactate accumulation. Consistent with cytochrome oxidase involvement, the glycolytic effect was enhanced at a low oxygen level and became irreversible at a high NO concentration or after prolonged exposure. Measurements of both glycolytic rate and mitochondrial pyruvate consumption revealed significant effects even at nanomolar NO concentrations. We conclude that NO can modulate astrocytic energy metabolism in the short term, reversibly, and at concentrations known to be released by endothelial cells under physiological conditions. These findings suggest that NO modulates the size of the astrocytic lactate reservoir involved in neuronal fueling and signaling. PMID:28341740

Nanomolar nitric oxide concentrations quickly and reversibly modulate astrocytic energy metabolism.

PubMed

San Martín, Alejandro; Arce-Molina, Robinson; Galaz, Alex; Pérez-Guerra, Gustavo; Barros, L Felipe

2017-06-02

Nitric oxide (NO) is an intercellular messenger involved in multiple bodily functions. Prolonged NO exposure irreversibly inhibits respiration by covalent modification of mitochondrial cytochrome oxidase, a phenomenon of pathological relevance. However, the speed and potency of NO's metabolic effects at physiological concentrations are incompletely characterized. To this end, we set out to investigate the metabolic effects of NO in cultured astrocytes from mice by taking advantage of the high spatiotemporal resolution afforded by genetically encoded Förster resonance energy transfer (FRET) nanosensors. NO exposure resulted in immediate and reversible intracellular glucose depletion and lactate accumulation. Consistent with cytochrome oxidase involvement, the glycolytic effect was enhanced at a low oxygen level and became irreversible at a high NO concentration or after prolonged exposure. Measurements of both glycolytic rate and mitochondrial pyruvate consumption revealed significant effects even at nanomolar NO concentrations. We conclude that NO can modulate astrocytic energy metabolism in the short term, reversibly, and at concentrations known to be released by endothelial cells under physiological conditions. These findings suggest that NO modulates the size of the astrocytic lactate reservoir involved in neuronal fueling and signaling. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

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.

Psychotherapy and Pharmacotherapy for Patients with Dissociative Identity Disorder

PubMed Central

Gentile, Julie P.; Dillon, Kristy S.

2013-01-01

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

Functional (dissociative) retrograde amnesia.

PubMed

Markowitsch, H J; Staniloiu, A

2016-01-01

Retrograde amnesia is described as condition which can occur after direct brain damage, but which occurs more frequently as a result of a psychiatric illness. In order to understand the amnesic condition, content-based divisions of memory are defined. The measurement of retrograde memory is discussed and the dichotomy between "organic" and "psychogenic" retrograde amnesia is questioned. Briefly, brain damage-related etiologies of retrograde amnesia are mentioned. The major portion of the review is devoted to dissociative amnesia (also named psychogenic or functional amnesia) and to the discussion of an overlap between psychogenic and "brain organic" forms of amnesia. The "inability of access hypothesis" is proposed to account for most of both the organic and psychogenic (dissociative) patients with primarily retrograde amnesia. Questions such as why recovery from retrograde amnesia can occur in retrograde (dissociative) amnesia, and why long-term new learning of episodic-autobiographic episodes is possible, are addressed. It is concluded that research on retrograde amnesia research is still in its infancy, as the neural correlates of memory storage are still unknown. It is argued that the recollection of episodic-autobiographic episodes most likely involves frontotemporal regions of the right hemisphere, a region which appears to be hypometabolic in patients with dissociative amnesia. © 2016 Elsevier B.V. All rights reserved.

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.

Clandestine psychopathology: unrecognized dissociative disorders in inpatient psychiatry.

PubMed

Ginzburg, Karni; Somer, Eli; Tamarkin, Gali; Kramer, Lilach

2010-05-01

Surveys among Israeli mental health professionals found that almost half of them doubt the validity of dissociative disorders (DD) and have no experience in either diagnosing or treating DD patients. These findings, in line with arguments that DDs are socially construed North American phenomena, call for the need to investigate it in Israel. Eighty-one psychiatric inpatients were screened for dissociative pathology. Participants categorized as having low levels of dissociation (n = 26) and those demonstrating high levels of dissociation (n = 22) were asked to participate in a Structured Clinical Interview for the DSM-Dissociative Disorders-Revised. One-quarter of all participants were identified as having probable dissociative psychopathology. Based on the Structured Clinical Interview for the DSM-Dissociative Disorders-Revised, estimates of DD range between 12 and 21%. None of the participants had any indication of a DD diagnosis in their medical records. Diagnosis of personality disorder and psychiatric comorbidity were related to the likelihood of a DD diagnosis and its severity.

Dissociation kinetics of Fe(III)- and Al(III)-natural organic matter complexes at pH 6.0 and 8.0 and 25 °C

NASA Astrophysics Data System (ADS)

Jones, Adele M.; Pham, A. Ninh; Collins, Richard N.; Waite, T. David

2009-05-01

The rate at which iron- and aluminium-natural organic matter (NOM) complexes dissociate plays a critical role in the transport of these elements given the readiness with which they hydrolyse and precipitate. Despite this, there have only been a few reliable studies on the dissociation kinetics of these complexes suggesting half-times of some hours for the dissociation of Fe(III) and Al(III) from a strongly binding component of NOM. First-order dissociation rate constants are re-evaluated here at pH 6.0 and 8.0 and 25 °C using both cation exchange resin and competing ligand methods for Fe(III) and a cation exchange resin method only for Al(III) complexes. Both methods provide similar results at a particular pH with a two-ligand model accounting satisfactorily for the dissociation kinetics results obtained. For Fe(III), half-times on the order of 6-7 h were obtained for dissociation of the strong component and 4-5 min for dissociation of the weak component. For aluminium, the half-times were on the order of 1.5 h and 1-2 min for the strong and weak components, respectively. Overall, Fe(III) complexes with NOM are more stable than analogous complexes with Al(III), implying Fe(III) may be transported further from its source upon dilution and dispersion.

Effects of Charge State on Fragmentation Pathways, Dynamics, and Activation Energies of Ubiquitin Ions Measured by Blackbody Infrared Radiative Dissociation

PubMed Central

Jockusch, Rebecca A.; Schnier, Paul D.; Price, William D.; Strittmatter, Eric. F.; Demirev, Plamen A.; Williams*, Evan R.

2005-01-01

Blackbody infrared radiative dissociation spectra of the (M + 5H)5+ through (M + 11H)11+ ions of the protein ubiquitin (8.6 kDa) formed by electrospray ionization were measured in a Fourier-transform mass spectrometer. The 5+ ion dissociates exclusively by loss of water and/or ammonia, whereas the 11+ charge state dissociates only by formation of complementary y and b ions. These two processes are competitive for intermediate charge state ions, with the formation of y and b ions increasingly favored for the higher charge states. The y and b ions are formed by cleavage of the backbone amide bond on the C-terminal side of acidic residues exclusively, with cleavage adjacent to aspartic acid favored. Thermal unimolecular dissociation rate constants for the dissociation of each of these charge states were measured. From the temperature dependence of these rates, Arrhenius activation parameters in the rapid energy exchange limit are obtained. The activation energies (Ea) and preexponential factors (A) for the 5+, 8+, and 9+ ions are 1.2 eV and 1012 s−1, respectively. These values for the 6+ and 7+ ions are 0.9–1.0 eV and 109 s−1, and those for the 10+ and 11+ ions are 1.6 eV and 1016–1017 s−1. Thus, with the exception of the 5+ ion, the higher charge states of ubiquitin have larger dissociation activation energies than the lower charge states. The different A factors observed for production of y and b ions from different precursor charge states indicate that they are formed by different mechanisms, ranging from relatively complex rearrangements to direct bond cleavages. These results clearly demonstrate that the relative dissociation rates of large biomolecule ions by themselves are not necessarily a reliable indicator of their relative dissociation energies, even when similar fragment ions are formed. PMID:9075403

Effects of charge state on fragmentation pathways, dynamics, and activation energies of ubiquitin ions measured by blackbody infrared radiative dissociation.

PubMed

Jockusch, R A; Schnier, P D; Price, W D; Strittmatter, E F; Demirev, P A; Williams, E R

1997-03-15

Blackbody infrared radiative dissociation spectra of the (M + 5H)5+ through (M + 11H)11+ ions of the protein ubiquitin (8.6 kDa) formed by electrospray ionization were measured in a Fourier-transform mass spectrometer. The 5+ ion dissociates exclusively by loss of water and/or ammonia, whereas the 11+ charge state dissociates only by formation of complementary y and b ions. These two processes are competitive for intermediate charge state ions, with the formation of y and b ions increasingly favored for the higher charge states. The y and b ions are formed by cleavage of the backbone amide bond on the C-terminal side of acidic residues exclusively, with cleavage adjacent to aspartic acid favored. Thermal unimolecular dissociation rate constants for the dissociation of each of these charge states were measured. From the temperature dependence of these rates, Arrhenius activation parameters in the rapid energy exchange limit are obtained. The activation energies (Ea) and preexponential factors (A) for the 5+, 8+, and 9+ ions are 1.2 eV and 10(12) s-1, respectively. These values for the 6+ and 7+ ions are 0.9-1.0 eV and 10(9) s-1, and those for the 10+ and 11+ ions are 1.6 eV and 10(16)-10(17) s-1. Thus, with the exception of the 5+ ion, the higher charge states of ubiquitin have larger dissociation activation energies than the lower charge states. The different A factors observed for production of y and b ions from different precursor charge states indicate that they are formed by different mechanisms, ranging from relatively complex rearrangements to direct bond cleavages. These results clearly demonstrate that the relative dissociation rates of large biomolecule ions by themselves are not necessarily a reliable indicator of their relative dissociation energies, even when similar fragment ions are formed.

Exploring evidence of a dissociative subtype in PTSD: Baseline symptom structure, etiology, and treatment efficacy for those who dissociate.

PubMed

Burton, Mark S; Feeny, Norah C; Connell, Arin M; Zoellner, Lori A

2018-05-01

With the inclusion of a dissociative subtype, recent changes to the DSM-5 diagnosis of posttraumatic stress disorder (PTSD) have emphasized the role of dissociation in the experience and treatment of the disorder. However, there is a lack of research exploring the clinical impact for highly dissociative groups receiving treatment for PTSD. The current study examined the presence and clinical impact of a dissociative subtype in a sample of individuals receiving treatment for chronic PTSD. This study used latent transition analyses (LTA), an expanded form of latent profile analyses (LPA), to examine latent profiles of PTSD and dissociation symptoms before and after treatment for individuals (N = 200) receiving prolonged exposure (PE) or sertraline treatment for chronic PTSD. The best fitting LTA model was one with a 4-class solution at both pretreatment and posttreatment. There was a latent class at pretreatment with higher levels of dissociative symptoms. However, this class was also marked by higher reexperiencing symptoms, and membership was not predicted by chronic child abuse. Further, although those in the class were less likely to transition to the responder class overall, this was not the case for exposure-based treatment specifically. These findings are not in line with the dissociative-subtype theoretical literature that proposes those who dissociate represent a clinically distinct group that may respond worse to exposure-based treatments for PTSD. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Determining the folding and unfolding rate constants of nucleic acids by biosensor. Application to telomere G-quadruplex.

PubMed

Zhao, Yong; Kan, Zhong-yuan; Zeng, Zhi-xiong; Hao, Yu-hua; Chen, Hua; Tan, Zheng

2004-10-20

Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand.

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.

Does dissociation offer a useful explanation for psychopathology?

PubMed

Jureidini, Jon

2004-01-01

Dissociation is often conceptualised as an altered state of consciousness, a trance-like state in which normal barriers between conscious and unconscious memories, desires and beliefs break down and other amnestic barriers emerge. This review explores whether it is likely that there is a neurophysiology of pathological dissociative processes that will elucidate management. A critical reading of current research, sourced through Medline and Psychinfo searches from 1990 to 2002, using subject headings: dissociative disorders, hypnosis and stress disorder (post-traumatic), as well as keywords: dissociation, hypnosis and trance. Current knowledge does not support the notion of dissociation as a discrete brain state or process. Psychiatric and neurophysiological research and theory development are better directed towards individual components that contribute to dissociative experience. Copyright (c) 2004 S. Karger AG, Basel.

Measurement of threshold temperature effects in dissociative electron attachment to HI and DI

NASA Technical Reports Server (NTRS)

Chutjian, A.; Alajajian, S. H.; Man, K.-F.

1990-01-01

From accurate spectroscopic constants it is found that the thermal dissociative-attachment process (DA) in DI should be exothermic only for rotational levels J greater than 8 in v = O. Here, measurement of an enhancement of DA with rotational temperature T in the range 298-468 K is reported. The effect is easily accounted for by the increase in total fractional population of excited J levels in DI relative to HI. The effect affords a rotational analog to the use of vibrationally excited molecules (e.g., HCl) in a plasma to control electron conduction.

Rate coefficients for dissociative attachment and resonant electron-impact dissociation involving vibrationally excited O{sub 2} molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Rate coefficients for dissociative electron attachment and electron-impact dissociation processes, involving vibrationally excited molecular oxygen, are presented. Analytical fits of the calculated numerical data, useful in the applications, are also provided.

Hypnotic suggestibility, cognitive inhibition, and dissociation.

PubMed

Dienes, Zoltán; Brown, Elizabeth; Hutton, Sam; Kirsch, Irving; Mazzoni, Giuliana; Wright, Daniel B

2009-12-01

We examined two potential correlates of hypnotic suggestibility: dissociation and cognitive inhibition. Dissociation is the foundation of two of the major theories of hypnosis and other theories commonly postulate that hypnotic responding is a result of attentional abilities (including inhibition). Participants were administered the Waterloo-Stanford Group Scale of Hypnotic Susceptibility, Form C. Under the guise of an unrelated study, 180 of these participants also completed: a version of the Dissociative Experiences Scale that is normally distributed in non-clinical populations; a latent inhibition task, a spatial negative priming task, and a memory task designed to measure negative priming. The data ruled out even moderate correlations between hypnotic suggestibility and all the measures of dissociation and cognitive inhibition overall, though they also indicated gender differences. The results are a challenge for existing theories of hypnosis.

Dissociation, shame, complex PTSD, child maltreatment and intimate relationship self-concept in dissociative disorder, chronic PTSD and mixed psychiatric groups.

PubMed

Dorahy, Martin J; Middleton, Warwick; Seager, Lenaire; McGurrin, Patrick; Williams, Mary; Chambers, Ron

2015-02-01

Whilst a growing body of research has examined dissociation and other psychiatric symptoms in severe dissociative disorders (DDs), there has been no systematic examination of shame and sense of self in relationships in DDs. Chronic child abuse often associated with severe DDs, like dissociative identity disorder, is likely to heighten shame and relationship concerns. This study investigated complex posttraumatic stress disorder (PTSD), borderline and Schneiderian symptoms, dissociation, shame, child abuse, and various markers of self in relationships (e.g., relationship esteem, relationship depression, fear of relationships). Participants were assessed via clinical interview with psychometrically sound questionnaires. They fell into three diagnostic groups, dissociative disorder (n=39; primarily dissociative identity disorder), chronic PTSD (Chr-PTSD; n=13) or mixed psychiatric presentations (MP; n=21; primarily mood and anxiety disorders). All participants had a history of child abuse and/or neglect, and the groups did not differ on age and gender. The DD group was higher on nearly all measured variables than the MP group, and had more severe dissociative, borderline and Schneiderian symptoms than the Chr-PTSD sample. Shame and complex PTSD symptoms fell marginally short of predicting reductions in relationship esteem, pathological dissociative symptoms predicted increased relationship depression, and complex PTSD symptoms predicted fear of relationships. The representativeness of the samples was unknown. Severe psychiatric symptoms differentiate DDs from chronic PTSD, while dissociation and shame have a meaningful impact on specific markers of relationship functioning in psychiatric patients with a history of child abuse and neglect. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Trends in water monomer adsorption and dissociation on flat insulating surfaces.

PubMed

Hu, Xiao Liang; Carrasco, Javier; Klimeš, Jiří; Michaelides, Angelos

2011-07-21

The interaction of water with solid surfaces is key to a wide variety of industrial and natural processes. However, the basic principles that dictate how stable and in which state (intact or dissociated) water will be on a given surface are not fully understood. Towards this end, we have used density functional theory to examine water monomer adsorption on the (001) surfaces of a broad range of alkaline earth oxides, alkaline earth sulfides, alkali fluorides, and alkali chlorides. Some interesting general conclusions are arrived at: (i) on all the surfaces considered only a few specific adsorption structures are favoured; (ii) water becomes more stable upon descending the oxide and fluoride series but does not vary much upon going down the chloride and sulfide series; (iii) water is stabilised both by an increase in the lattice constant, which facilitates hydrogen bonding to the substrate, and by the flexibility of the substrate. These are also factors that favour water dissociation. We hope that this study is of some value in better understanding the surface science of water in general, and in assisting in the interpretation and design of future experiments. This journal is © the Owner Societies 2011

Development and Preliminary Psychometric Properties of an Instrument for the Measurement of Obsessional Dissociative Experiences: The Van Obsessional Dissociation Questionnaire (VOD-Q).

PubMed

Boysan, Murat; Yıldırım, Abdullah; Beşiroğlu, Lütfullah; Kefeli, Mehmet Celal; Kağan, Mücahit

2018-01-04

A growing body of research evidence documents the substantial associations between obsessive-compulsive disorder (OCD) and dissociation. This article describes the development and preliminary psychometric properties of the Van Obsessional Dissociation Questionnaire (VOD-Q). Obsessional dissociation is defined as a tendency to dissociate in reaction to distressing, unwanted and intrusive thoughts, images and impulses. The screening tool is conceptualized to tap obsessional dissociation across three dimensions: obsessional absorption, obsessional depersonalization/ derealization and obsessional amnesia. The VOD-Q, the Padua Inventory-Revised (PI-R), the Dissociative Experiences Scale (DES), and the Obsessive Belief Questionnaire (OBQ-44) were administered in this study. The results showed that the VOD-Q had excellent test-retest reliability (ranging from 0.73 to 0.90) and internal consistency (ranging from 0.90 to 0.97). The VOD-Q total and subscale scores were significantly associated with measures of obsessive-compulsive symptoms and dissociative experiences. OCD patients scored significantly higher on the VOD-Q than community participants. Based on the present findings, the VOD-Q appears to be a reliable and valid instrument for the measurement of obsessional dissociative experiences.

[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

Rate constants for chemical reactions in high-temperature nonequilibrium air

NASA Technical Reports Server (NTRS)

Jaffe, R. L.

1986-01-01

In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.

Influence of Coulombic repulsion on the dissociation pathways and energetics of multiprotein complexes in the gas phase.

PubMed

Sinelnikov, Igor; Kitova, Elena N; Klassen, John S

2007-04-01

Thermal dissociation experiments, implemented with blackbody infrared radiative dissociation and Fourier-transform ion cyclotron resonance mass spectrometry, are performed on gaseous protonated and deprotonated ions of the homopentameric B subunits of Shiga toxin 1 (Stx1 B5) and Shiga toxin 2 (Stx2 B5) and the homotetramer streptavidin (S4). Dissociation of the gaseous, multisubunit complexes proceeds predominantly by the loss of a single subunit. Notably, the fractional partitioning of charge between the product ions, i.e., the leaving subunit and the resulting multimer, for a given complex is, within error, constant over the range of charge states investigated. The Arrhenius activation parameters (E(a), A) measured for the loss of subunit decrease with increasing charge state of the complex. However, the parameters for the protonated and deprotonated ions, with the same number of charges, are indistinguishable. The influence of the complex charge state on the dissociation pathways and the magnitude of the dissociation E(a) are modeled theoretically with the discrete charge droplet model (DCDM) and the protein structure model (PSM), wherein the structure of the subunits is considered. Importantly, the major subunit charge states observed experimentally for the Stx1 B5(n+/-) ions correspond to the minimum energy charge distribution predicted by DCDM and PSM assuming a late dissociative transition-state (TS); while for structurally-related Stx2 B5(n+) ions, the experimental charge distribution corresponds to an early TS. It is proposed that the lateness of the TS is related, in part, to the degree of unfolding of the leaving subunit, with Stx1 B being more unfolded than Stx2 B. PSM, incorporating significant subunit unfolding is necessary to account for the product ions observed for the S4(n+) ions. The contribution of Coulombic repulsion to the dissociation E(a) is quantified and the intrinsic activation energy is estimated for the first time.

Kinetic rate constant prediction supports the conformational selection mechanism of protein binding.

PubMed

Moal, Iain H; Bates, Paul A

2012-01-01

The prediction of protein-protein kinetic rate constants provides a fundamental test of our understanding of molecular recognition, and will play an important role in the modeling of complex biological systems. In this paper, a feature selection and regression algorithm is applied to mine a large set of molecular descriptors and construct simple models for association and dissociation rate constants using empirical data. Using separate test data for validation, the predicted rate constants can be combined to calculate binding affinity with accuracy matching that of state of the art empirical free energy functions. The models show that the rate of association is linearly related to the proportion of unbound proteins in the bound conformational ensemble relative to the unbound conformational ensemble, indicating that the binding partners must adopt a geometry near to that of the bound prior to binding. Mirroring the conformational selection and population shift mechanism of protein binding, the models provide a strong separate line of evidence for the preponderance of this mechanism in protein-protein binding, complementing structural and theoretical studies.

A latent class analysis of dissociation and posttraumatic stress disorder: evidence for a dissociative subtype.

PubMed

Wolf, Erika J; Miller, Mark W; Reardon, Annemarie F; Ryabchenko, Karen A; Castillo, Diane; Freund, Rachel

2012-07-01

The nature of the relationship of dissociation to posttraumatic stress disorder (PTSD) is controversial and of considerable clinical and nosologic importance. To examine evidence for a dissociative subtype of PTSD and to examine its association with different types of trauma. A latent profile analysis of cross-sectional data from structured clinical interviews indexing DSM-IV symptoms of current PTSD and dissociation. The VA Boston Healthcare System and the New Mexico VA Health Care System. A total of 492 veterans and their intimate partners, all of whom had a history of trauma. Participants reported exposure to a variety of traumatic events, including combat, childhood physical and sexual abuse, partner abuse, motor vehicle accidents, and natural disasters, with most participants reporting exposure to multiple types of traumatic events. Forty-two percent of the sample met the criteria for a current diagnosis of PTSD. Item-level scores on the Clinician-Administered PTSD Scale. A latent profile analysis suggested a 3-class solution: a low PTSD severity subgroup, a high PTSD severity subgroup characterized by elevations across the 17 core symptoms of the disorder, and a small but distinctly dissociative subgroup that composed 12% of individuals with a current diagnosis of PTSD. The latter group was characterized by severe PTSD symptoms combined with marked elevations on items assessing flashbacks, derealization, and depersonalization. Individuals in this subgroup also endorsed greater exposure to childhood and adult sexual trauma compared with the other 2 groups, suggesting a possible etiologic link with the experience of repeated sexual trauma. These results support the subtype hypothesis of the association between PTSD and dissociation and suggest that dissociation is a highly salient facet of posttraumatic psychopathology in a subset of individuals with the disorder.

Kinetic Characterisation of a Single Chain Antibody against the Hormone Abscisic Acid: Comparison with Its Parental Monoclonal

PubMed Central

Badescu, George O.; Marsh, Andrew; Smith, Timothy R.; Thompson, Andrew J.; Napier, Richard M.

2016-01-01

A single-chain Fv fragment antibody (scFv) specific for the plant hormone abscisic acid (ABA) has been expressed in the bacterium Escherichia coli as a fusion protein. The kinetics of ABA binding have been measured using surface plasmon resonance spectrometry (BIAcore 2000) using surface and solution assays. Care was taken to calculate the concentration of active protein in each sample using initial rate measurements under conditions of partial mass transport limitation. The fusion product, parental monoclonal antibody and the free scFv all have low nanomolar affinity constants, but there is a lower dissociation rate constant for the parental monoclonal resulting in a three-fold greater affinity. Analogue specificity was tested and structure-activity binding preferences measured. The biologically-active (+)-ABA enantiomer is recognised with an affinity three orders of magnitude higher than the inactive (-)-ABA. Metabolites of ABA including phaseic acid, dihydrophaseic acid and deoxy-ABA have affinities over 100-fold lower than that for (+)-ABA. These properties of the scFv make it suitable as a sensor domain in bioreporters specific for the naturally occurring form of ABA. PMID:27023768

Tubulin Dimer Reversible Dissociation

PubMed Central

Schuck, Peter; Sackett, Dan L.

2016-01-01

Tubulins are evolutionarily conserved proteins that reversibly polymerize and direct intracellular traffic. Of the tubulin family only αβ-tubulin forms stable dimers. We investigated the monomer-dimer equilibrium of rat brain αβ-tubulin using analytical ultracentrifugation and fluorescence anisotropy, observing tubulin in virtually fully monomeric and dimeric states. Monomeric tubulin was stable for a few hours and exchanged into preformed dimers, demonstrating reversibility of dimer dissociation. Global analysis combining sedimentation velocity and fluorescence anisotropy yielded Kd = 84 (54–123) nm. Dimer dissociation kinetics were measured by analyzing the shape of the sedimentation boundary and by the relaxation of fluorescence anisotropy following rapid dilution of labeled tubulin, yielding koff in the range 10−3–10−2 s−1. Thus, tubulin dimers reversibly dissociate with moderately fast kinetics. Monomer-monomer association is much less sensitive than dimer-dimer association to solution changes (GTP/GDP, urea, and trimethylamine oxide). PMID:26934918

Psychophysiology of dissociated consciousness.

PubMed

Bob, Petr

2014-01-01

Recent study of consciousness provides an evidence that there is a limit of consciousness, which presents a barrier between conscious and unconscious processes. This barrier likely is specifically manifested as a disturbance of neural mechanisms of consciousness that through distributed brain processing, attentional mechanisms and memory processes enable to constitute integrative conscious experience. According to recent findings a level of conscious integration may change during certain conditions related to experimental cognitive manipulations, hypnosis, or stressful experiences that can lead to dissociation of consciousness. In psychopathological research the term dissociation was proposed by Pierre Janet for explanation of processes related to splitting of consciousness due to traumatic events or during hypnosis. According to several recent findings dissociation of consciousness likely is related to deficits in global distribution of information and may lead to heightened levels of "neural complexity" that reflects brain integration or differentiation based on numbers of independent neural processes in the brain that may be specifically related to various mental disorders.

Assessment of dissociation in Bosnian treatment-seeking refugees in Denmark.

PubMed

Palic, Sabina; Carlsson, Jessica; Armour, Cherie; Elklit, Ask

2015-05-01

Dissociative experiences are common in traumatized individuals, and can sometimes be mistaken for psychosis. It is difficult to identify pathological dissociation in the treatment of traumatized refugees, because there is a lack of systematic clinical descriptions of dissociative phenomena in refugees. Furthermore, we are currently unaware of how dissociation measures perform in this clinical group. To describe the phenomenology of dissociative symptoms in Bosnian treatment-seeking refugees in Denmark. As a part of a larger study, dissociation was assessed systematically in 86 Bosnian treatment-seeking refugees using a semi-structured clinical interview (Structured Interview for Disorders of Extreme Stress-dissociation subscale; SIDES-D) and a self-report scale (Dissociative Experiences Scale; DES). The SIDES-D indicated twice as high prevalence of pathological dissociation as the DES. According to the DES, 30% of the refugees had pathological dissociation 15 years after their resettlement. On the SIDES-D, depersonalization and derealization experiences were the most common. Also, questions about depersonalization and derealization at times elicited reporting of visual and perceptual hallucinations, which were unrelated to traumatic re-experiencing. Questions about personality alteration elicited spontaneous reports of a phenomenon of "split" pre- and post-war identity in the refugee group. Whether this in fact is a dissociative phenomenon, characteristic of severe traumatization in adulthood, needs further examination. Knowledge of dissociative symptoms in traumatized refugees is important in clinical settings to prevent misclassification and to better target psychotherapeutic interventions. Much development in the measurement of dissociation in refugees is needed.

Cobalt porphyrin-mediated oxygen transport in a polymer membrane. Effect of the cobalt porphyrin structure on the oxygen-binding reaction, oxygen-diffusion constants, and oxygen-transport efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nishide, Hiroyuki; Suzuki, Takayuki; Kawakami, Hiroyoshi

1994-05-12

New derivatives of (meso-[alpha],[alpha],[alpha],[alpha]-tetrakis(o-pivalamidophenyl)porphinato)cobalt (CoPs) were characterized by oxygen-binding equilibrium and rate constants of the cobalt centered in the porphyrins. They depended on the structure of the porphyrin; for example, the rate constants of oxygen binding and dissociation (k[sub on] and k[sub off]) for [alpha][sup 3][beta]-CoP[sub 4]P were 3 and 20 times as large as those for [alpha][sup 4]-CoB[sub 4]P, respectively. Oxygen transport through the polymer membranes containing CoPs as the fixed oxygen carriers was facilitated and was affected by the oxygen-binding character or the structure of CoPs. The logarithmically linear correlation of the oxygen-dissociation rate constant of CoPs (k[submore » off] = (3-66) x 10[sup 3] S[sup [minus]1]) with the diffusion constant of oxygen via CoPs fixed in the membranes (D[sub cc] = (3-140) x 10[sup [minus]9] cm[sup 2] s[sup [minus]1]) was given for those six CoP derivatives. 26 refs., 5 figs., 2 tabs.« less

People reporting experiences of mediumship have higher dissociation symptom scores than non-mediums, but below thresholds for pathological dissociation

PubMed Central

Wahbeh, Helané; Radin, Dean

2018-01-01

Background: Dissociative states exist on a continuum from nonpathological forms, such as highway hypnosis and day-dreaming, to pathological states of derealization and depersonalization. Claims of communication with deceased individuals, known as mediumship, were once regarded as a pathological form of dissociation, but current definitions recognize the continuum and include distress and functional disability as symptoms of pathology. This study examined the relationship between dissociative symptoms and mediumship in a large convenience sample. Methods: Secondary analyses of cross-sectional survey data were conducted. The survey included demographics, the Dissociation Experience Scale Taxon (DES-T, score range 0-100), as well as questions about instances of mediumship experiences. Summary statistics and linear and logistic regressions explored the relationship between dissociative symptoms and mediumship endorsement. Results: 3,023 participants were included and were mostly middle-aged (51 years ± 16; range 17-96), female (70%), Caucasian (85%), college educated (88%), had an annual income over $50,000 (55%), and were raised Christian (71%) but were presently described as Spiritual but not Religious (60%). Mediumship experiences were endorsed by 42% of participants, the experiences usually began in childhood (81%), and 53% had family members who reported similar experiences. The mean DES-T score across all participants was 14.4 ± 17.3, with a mean of 18.2 ± 19.3 for those claiming mediumship experiences and 11.8 ± 15.2 for those who did not (t = -10.3, p < 0.0005). The DES-T threshold score for pathological dissociation is 30. Conclusions: On average, individuals claiming mediumship experiences had higher dissociation scores than non-claimants, but neither group exceeded the DES-T threshold for pathology. Future studies exploring dissociative differences between these groups may benefit from using more comprehensive measures of dissociative symptoms as well as

The Parenting Experiences of Mothers with Dissociative Disorders.

ERIC Educational Resources Information Center

Benjamin, Lynn R.; Benjamin, Robert; Rind, Bruce

1998-01-01

Presents a qualitative analysis of the experience of parenting of mothers with dissociative disorders. Using the mothers' words, describes how the five symptom areas of dissociation impeded their parenting efforts. Discusses the necessity of addressing parenting in the treatment of client-mothers with dissociative disorders. (Author/MKA)

Supplementation with nanomolar concentrations of verbascoside during in vitro maturation improves embryo development by protecting the oocyte against oxidative stress: a large animal model study.

PubMed

Martino, Nicola Antonio; Ariu, Federica; Bebbere, Daniela; Uranio, Manuel Filioli; Chirico, Adriana; Marzano, Giuseppina; Sardanelli, Anna Maria; Cardinali, Angela; Minervini, Fiorenza; Bogliolo, Luisa; Dell'Aquila, Maria Elena

2016-10-01

The effects of verbascoside (VB), added at nanomolar concentrations during in vitro maturation (IVM) of juvenile sheep oocytes, on in vitro embryo development and its mechanisms of action at the oocyte level were analyzed. Developmental rates, after IVM in the presence/absence of VB (1nM for 24h; 1nM for 2h; 10nM for 2h), were evaluated. The bioenergetic/oxidative status of oocytes matured after IVM in the presence/absence of 1nM VB for 24h was assessed by confocal analysis of mitochondria and reactive oxygen species (ROS), lipid peroxidation (LPO) assay, and quantitative PCR of bioenergy/redox-related genes. The addition of 1nM VB during 24h IVM significantly increased blastocyst formation and quality. Verbascoside reduced oocyte ROS and LPO and increased mitochondria/ROS colocalization while keeping mitochondria activity and gene expression unchanged. In conclusion, supplementation with nanomolar concentrations of VB during IVM, in the juvenile sheep model, promotes embryo development by protecting the oocyte against oxidative stress. Copyright © 2016 Elsevier Inc. All rights reserved.

Acyl guanidine inhibitors of β-secretase (BACE-1): optimization of a micromolar hit to a nanomolar lead via iterative solid- and solution-phase library synthesis.

PubMed

Gerritz, Samuel W; Zhai, Weixu; Shi, Shuhao; Zhu, Shirong; Toyn, Jeremy H; Meredith, Jere E; Iben, Lawrence G; Burton, Catherine R; Albright, Charles F; Good, Andrew C; Tebben, Andrew J; Muckelbauer, Jodi K; Camac, Daniel M; Metzler, William; Cook, Lynda S; Padmanabha, Ramesh; Lentz, Kimberley A; Sofia, Michael J; Poss, Michael A; Macor, John E; Thompson, Lorin A

2012-11-08

This report describes the discovery and optimization of a BACE-1 inhibitor series containing an unusual acyl guanidine chemotype that was originally synthesized as part of a 6041-membered solid-phase library. The synthesis of multiple follow-up solid- and solution-phase libraries facilitated the optimization of the original micromolar hit into a single-digit nanomolar BACE-1 inhibitor in both radioligand binding and cell-based functional assay formats. The X-ray structure of representative inhibitors bound to BACE-1 revealed a number of key ligand:protein interactions, including a hydrogen bond between the side chain amide of flap residue Gln73 and the acyl guanidine carbonyl group, and a cation-π interaction between Arg235 and the isothiazole 4-methoxyphenyl substituent. Following subcutaneous administration in rats, an acyl guanidine inhibitor with single-digit nanomolar activity in cells afforded good plasma exposures and a dose-dependent reduction in plasma Aβ levels, but poor brain exposure was observed (likely due to Pgp-mediated efflux), and significant reductions in brain Aβ levels were not obtained.

Childhood Trauma and Dissociative Intimate Partner Violence.

PubMed

Webermann, Aliya R; Murphy, Christopher M

2018-04-01

The present study assesses childhood abuse/neglect as a predictor of dissociative intimate partner violence (IPV) among 118 partner-abusive men. One third (36%) endorsed dissociative IPV, most commonly losing control (18%), surroundings seeming unreal (16%), feeling someone other than oneself is aggressing (16%), and seeing oneself from a distance aggressing (10%). Childhood physical abuse/neglect predicted IPV-specific derealization/depersonalization, aggressive self-states, and flashbacks to past violence. Childhood emotional abuse/neglect predicted derealization/depersonalization, blackouts, and flashbacks. Childhood sexual abuse uniquely predicted amnesia. Other potential traumas did not predict dissociative IPV, suggesting dissociative IPV is influenced by trauma-based emotion dysregulation wherein childhood abuse/neglect survivors disconnect from their abusive behavior.

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…

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-02-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

Electron Transfer Dissociation and Collision-Induced Dissociation of Underivatized Metallated Oligosaccharides

NASA Astrophysics Data System (ADS)

Schaller-Duke, Ranelle M.; Bogala, Mallikharjuna R.; Cassady, Carolyn J.

2018-05-01

Electron transfer dissociation (ETD) and collision-induced dissociation (CID) were used to investigate underivatized, metal-cationized oligosaccharides formed via electrospray ionization (ESI). Reducing and non-reducing sugars were studied including the tetrasaccharides maltotetraose, 3α,4β,3α-galactotetraose, stachyose, nystose, and a heptasaccharide, maltoheptaose. Univalent alkali, divalent alkaline earth, divalent and trivalent transition metal ions, and a boron group trivalent metal ion were adducted to the non-permethylated oligosaccharides. ESI generated [M + Met]+, [M + 2Met]2+, [M + Met]2+, [M + Met - H]+, and [M + Met - 2H]+ most intensely along with low intensity nitrate adducts, depending on the metal and sugar ionized. The ability of these metal ions to produce oligosaccharide adduct ions by ESI had the general trend: Ca(II) > Mg(II) > Ni(II) > Co(II) > Zn(II) > Cu(II) > Na(I) > K(I) > Al(III) ≈ Fe(III) ≈ Cr(III). Although trivalent metals were utilized, no triply charged ions were formed. Metal cations allowed for high ESI signal intensity without permethylation. ETD and CID on [M + Met]2+ produced various glycosidic and cross-ring cleavages, with ETD producing more cross-ring and internal ions, which are useful for structural analysis. Product ion intensities varied based on glycosidic-bond linkage and identity of monosaccharide sub-unit, and metal adducts. ETD and CID showed high fragmentation efficiency, often with complete precursor dissociation, depending on the identity of the adducted metal ion. Loss of water was occasionally observed, but elimination of small neutral molecules was not prevalent. For both ETD and CID, [M + Co]2+ produced the most uniform structurally informative dissociation with all oligosaccharides studied. The ETD and CID spectra were complementary. [Figure not available: see fulltext.

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.

Pain, dissociation and subliminal self-representations.

PubMed

Bob, Petr

2008-03-01

According to recent evidence, neurophysiological processes coupled to pain are closely related to the mechanisms of consciousness. This evidence is in accordance with findings that changes in states of consciousness during hypnosis or traumatic dissociation strongly affect conscious perception and experience of pain, and markedly influence brain functions. Past research indicates that painful experience may induce dissociated state and information about the experience may be stored or processed unconsciously. Reported findings suggest common neurophysiological mechanisms of pain and dissociation and point to a hypothesis of dissociation as a defense mechanism against psychological and physical pain that substantially influences functions of consciousness. The hypothesis is also supported by findings that information can be represented in the mind/brain without the subject's awareness. The findings of unconsciously present information suggest possible binding between conscious contents and self-functions that constitute self-representational dimensions of consciousness. The self-representation means that certain inner states of own body are interpreted as mental and somatic identity, while other bodily signals, currently not accessible to the dominant interpreter's access are dissociated and may be defined as subliminal self-representations. In conclusion, the neurophysiological aspects of consciousness and its integrative role in the therapy of painful traumatic memories are discussed.

Assessing the structure and meaningfulness of the dissociative subtype of PTSD.

PubMed

Ross, Jana; Baník, Gabriel; Dědová, Mária; Mikulášková, Gabriela; Armour, Cherie

2018-01-01

Studies conducted in the USA, Canada and Denmark have supported the existence of the dissociative PTSD subtype, characterized primarily by symptoms of depersonalization and derealization. The current study aimed to examine the dissociative PTSD subtype in an Eastern European, predominantly female (83.16%) sample, using an extended set of dissociative symptoms. A latent profile analysis was applied to the PTSD and dissociation data from 689 trauma-exposed university students from Slovakia. Four latent profiles of varying PTSD and dissociation symptomatology were uncovered. They were named non-symptomatic, moderate PTSD, high PTSD and dissociative PTSD. The dissociative PTSD profile showed elevations on depersonalization and derealization, but also the alternative dissociative indicators of gaps in awareness and memory, sensory misperceptions and cognitive and behavioural re-experiencing. The core PTSD symptoms of 'memory impairment' and 'reckless or self-destructive behaviour' were also significantly elevated in the dissociative PTSD profile. Moreover, anxiety and anger predicted membership in the dissociative PTSD profile. The results provide support for the proposal that the dissociative PTSD subtype can be characterized by a variety of dissociative symptoms.

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

Editorial: Dissociation in Pre-School Children.

ERIC Educational Resources Information Center

Jones, David P. H.

2001-01-01

This editorial comments on a study that compared the self-development of 43 typical preschool children and 155 preschool children who had been maltreated. It found sexually abused, physically abused, and neglected preschool children showed more dissociation than did the typical children. Clinically identifiable dissociation was particularly…

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.

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.

Parents' descriptions of young children's dissociative reactions after trauma.

PubMed

Cintron, Gabriela; Salloum, Alison; Blair-Andrews, Zoe; Storch, Eric A

2017-10-09

There is limited research on the phenomenology of how young children who have been exposed to trauma express the intrusive symptom of dissociative reactions. The current qualitative study utilized interviews from a semi-structured diagnostic clinical interview with 74 caregivers of young children (ages 3 to 7) who were exposed to trauma to identify parents' descriptions of their children's dissociative reactions during a clinical interview. Based on results from the interview, 45.9% of the children had dissociative reactions (8.5% had flashbacks and 41.9% had dissociative episodes). Interviews were transcribed to identify themes of dissociative reactions in young children. Common themes to flashbacks and dissociative episodes included being triggered, being psychologically in their own world (e.g., spaced out and shut down), and displaying visible signs (e.g., crying and screaming). For flashbacks, caregivers reported that it seemed as if the child was re-experiencing the trauma (e.g., yelling specific words and having body responses). For dissociative episodes, caregivers noted that the child not only seemed psychologically somewhere else (e.g., distant and not there) but also would be physically positioned somewhere else (e.g., sitting and not responding). Caregivers also expressed their own reactions to the child's dissociative episode due to not understanding what was occurring, and trying to interrupt the occurrences (e.g., calling out to the child). Themes, descriptions, and phrases to describe dissociative reactions in young children after trauma can be used to help parents and professionals more accurately identify occurrences of dissociative reactions.

Dissociative seizures--a critical review and perspective.

PubMed

Schmutz, Matthias

2013-12-01

Dissociative seizures are commonly recognized as both a challenging and a poorly understood condition. Though research and publication activity is high, advances in knowledge and insight seem only moderate in recent years. This review focuses on some relevant problematic issues, which might account for a still unsatisfactory research state. A general tendency to deal with dissociative seizures as an assumed disorder in its own nosological right and not as a sole symptom of an underlying psychiatric disorder is most likely one of the major roots of the problem. Unfavorable impacts of this confusion pertaining to clinical management, therapy, and outcome of dissociative seizures are discussed. An alternative point of view, based on the immanent psychiatric and psychodynamic roots of dissociative seizures, is considered. © 2013.

Dissociative features in posttraumatic stress disorder: A latent profile analysis.

PubMed

Műllerová, Jana; Hansen, Maj; Contractor, Ateka A; Elhai, Jon D; Armour, Cherie

2016-09-01

The fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) characterizes the dissociative subtype of posttraumatic stress disorder (PTSD) in terms of the individual meeting the criteria for PTSD and additionally reporting symptoms of depersonalization and/or derealization. The current study aimed to examine whether a dissociative PTSD profile may include alternative features of dissociation and whether it could be differentiated from a nondissociative PTSD profile on certain psychopathologies and demographics. Data from 309 trauma-exposed participants, collected through Amazon Mechanical Turk, were subjected to latent profile analysis. Regression analyses were used to examine the predictors of latent classes. Three discrete profiles named Baseline, PTSD, and Dissociative profile were uncovered. All examined features of dissociation were significantly elevated in the Dissociative profile. Anxiety, male sex, being employed, and having a minority racial background significantly predicted the Dissociative profile relative to the PTSD profile. The study points to the importance of alternative symptoms of dissociation in the dissociative PTSD subtype beyond the symptoms of depersonalization and derealization. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

Real-time electrical detection of nitric oxide in biological systems with sub-nanomolar sensitivity

NASA Astrophysics Data System (ADS)

Jiang, Shan; Cheng, Rui; Wang, Xiang; Xue, Teng; Liu, Yuan; Nel, Andre; Huang, Yu; Duan, Xiangfeng

2013-07-01

Real-time monitoring of nitric oxide concentrations is of central importance for probing the diverse roles of nitric oxide in neurotransmission, cardiovascular systems and immune responses. Here we report a new design of nitric oxide sensors based on hemin-functionalized graphene field-effect transistors. With its single atom thickness and the highest carrier mobility among all materials, graphene holds the promise for unprecedented sensitivity for molecular sensing. The non-covalent functionalization through π-π stacking interaction allows reliable immobilization of hemin molecules on graphene without damaging the graphene lattice to ensure the highly sensitive and specific detection of nitric oxide. Our studies demonstrate that the graphene-hemin sensors can respond rapidly to nitric oxide in physiological environments with a sub-nanomolar sensitivity. Furthermore, in vitro studies show that the graphene-hemin sensors can be used for the detection of nitric oxide released from macrophage cells and endothelial cells, demonstrating their practical functionality in complex biological systems.

High psychiatric comorbidity in adolescents with dissociative disorders.

PubMed

Bozkurt, Hasan; Duzman Mutluer, Tuba; Kose, Cigdem; Zoroglu, Salih

2015-06-01

The aim of this study was to evaluate psychiatric comorbidity rates and patterns in a sample of clinically referred adolescents diagnosed with dissociative disorders (DD) by using a structured interview. All participants completed a comprehensive test battery, which consisted of a questionnaire for sociodemographic data and clinical history, Child Posttraumatic Stress Reaction Index, Childhood Abuse and Neglect Questionnaire and the Adolescent Dissociative Experiences Scale. Diagnosis was made by the Structured Clinical Interview for DSM-IV Dissociative Disorders. Psychiatric comorbidity was assessed using the Schedule for Affective Disorders and Schizophrenia for School Age Children - Present and Lifetime Version. A total of 25 adolescent subjects aged 12-18 years participated in the study. Ten adolescents were diagnosed as having dissociative identity disorder and 15 of them were diagnosed as having dissociative disorder-not otherwise specified based on the Structured Clinical Interview for DSM-IV Dissociative Disorders findings. Adolescents with dissociative identity disorder were found to have higher scores on the Adolescent Dissociative Experiences Scale and Child Posttraumatic Stress Reaction Index than the dissociative disorder-not otherwise specified group. Sexual and physical abuses were also found to be among the main traumatic events. Incest was reported in six cases of the study sample. All subjects had at least one comorbid psychiatric disorder. The most common psychiatric diagnoses were major depressive disorder (n = 25; 100%) and post-traumatic stress disorder (n = 22; 88%). High psychiatric comorbidity rates were found in adolescents diagnosed with DD. A prevalent history of abuse and traumatic events was represented. Clinicians should be aware of the impacts of DD on adolescents' mental health. © 2014 The Authors. Psychiatry and Clinical Neurosciences © 2014 Japanese Society of Psychiatry and Neurology.

Interaction of chlorogenic acids and quinides from coffee with human serum albumin.

PubMed

Sinisi, Valentina; Forzato, Cristina; Cefarin, Nicola; Navarini, Luciano; Berti, Federico

2015-02-01

Chlorogenic acids and their derivatives are abundant in coffee and their composition changes between coffee species. Human serum albumin (HSA) interacts with this family of compounds with high affinity. We have studied by fluorescence spectroscopy the specific binding of HSA with eight compounds that belong to the coffee polyphenols family, four acids (caffeic acid, ferulic acid, 5-O-caffeoyl quinic acid, and 3,4-dimethoxycinnamic acid) and four lactones (3,4-O-dicaffeoyl-1,5-γ-quinide, 3-O-[3,4-(dimethoxy)cinnamoyl]-1,5-γ-quinide, 3,4-O-bis[3,4-(dimethoxy)cinnamoyl]-1,5-γ-quinide, and 1,3,4-O-tris[3,4-(dimethoxy)cinnamoyl]-1,5-γ-quinide), finding dissociation constants of the albumin-chlorogenic acids and albumin-quinides complexes in the micromolar range, between 2 and 30μM. Such values are comparable with those of the most powerful binders of albumin, and more favourable than the values obtained for the majority of drugs. Interestingly in the case of 3,4-O-dicaffeoyl-1,5-γ-quinide, we have observed the entrance of two ligand molecules in the same binding site, leading up to a first dissociation constant even in the hundred nanomolar range, which is to our knowledge the highest affinity ever observed for HSA and its ligands. The displacement of warfarin, a reference drug binding to HSA, by the quinide has also been demonstrated. Copyright © 2014 Elsevier Ltd. All rights reserved.

Highly affine and selective aptamers against cholera toxin as capture elements in magnetic bead-based sandwich ELAA.

PubMed

Frohnmeyer, Esther; Frisch, Farina; Falke, Sven; Betzel, Christian; Fischer, Markus

2018-03-10

Aptamers are single-stranded DNA or RNA oligonucleotides, which have been emerging as recognition elements in disease diagnostics and food control, including the detection of bacterial toxins. In this study, we employed the semi-automated just in time-selection to identify aptamers that bind to cholera toxin (CT) with high affinity and specificity. CT is the main virulence factor of Vibrio cholerae and the causative agent of the eponymous disease. For the selected aptamers, dissociation constants in the low nanomolar range (23-56 nM) were determined by fluorescence-based affinity chromatography and cross-reactivity against related proteins was evaluated by direct enzyme-linked aptamer assay (ELAA). Aptamer CT916 has a dissociation constant of 48.5 ± 0.5 nM and shows negligible binding to Shiga-like toxin 1B, protein A and BSA. This aptamer was chosen to develop a sandwich ELAA for the detection of CT from binding buffer and local tap water. Amine-C6- or biotin-modified CT916 was coupled to magnetic beads to serve as the capture element. Using an anti-CT polyclonal antibody as the reporter, detection limits of 2.1 ng/ml in buffer and 2.4 ng/ml in tap water, with a wide log-linear dynamic range from 1 ng/ml to 1000 ng/ml and 500 ng/ml, respectively, were achieved. Copyright © 2018 Elsevier B.V. All rights reserved.

Dissociative recombination of HCl+

NASA Astrophysics Data System (ADS)

Larson, Åsa; Fonseca dos Santos, Samantha; E. Orel, Ann

2017-08-01

The dissociative recombination of HCl+, including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0 , to the first three excited vibrational states, v = 1 , v = 2 , and v = 3 , are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

Dissociative recombination of HCl.

PubMed

Larson, Åsa; Fonseca Dos Santos, Samantha; E Orel, Ann

2017-08-28

The dissociative recombination of HCl + , including both the direct and indirect mechanisms, is studied. For the direct process, the relevant electronic states are calculated ab initio by combining electron scattering calculations to obtain resonance positions and autoionization widths with multi-reference configuration interaction calculations of the ion and Rydberg states. The cross section for the direct dissociation along electronic resonant states is computed by solution of the time-dependent Schrödinger equation. For the indirect process, an upper bound value for the cross section is obtained using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Vibrational excitations of the ionic core from the ground vibrational state, v = 0, to the first three excited vibrational states, v = 1, v = 2, and  v = 3, are considered. Autoionization is neglected and the effect of the spin-orbit splitting of the ionic potential energy upon the indirect dissociative recombination cross section is considered. The calculated cross sections are compared to measurements.

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.

Characterizing Changes in the Rate of Protein-Protein Dissociation upon Interface Mutation Using Hotspot Energy and Organization

PubMed Central

Agius, Rudi; Torchala, Mieczyslaw; Moal, Iain H.; Fernández-Recio, Juan; Bates, Paul A.

2013-01-01

Predicting the effects of mutations on the kinetic rate constants of protein-protein interactions is central to both the modeling of complex diseases and the design of effective peptide drug inhibitors. However, while most studies have concentrated on the determination of association rate constants, dissociation rates have received less attention. In this work we take a novel approach by relating the changes in dissociation rates upon mutation to the energetics and architecture of hotspots and hotregions, by performing alanine scans pre- and post-mutation. From these scans, we design a set of descriptors that capture the change in hotspot energy and distribution. The method is benchmarked on 713 kinetically characterized mutations from the SKEMPI database. Our investigations show that, with the use of hotspot descriptors, energies from single-point alanine mutations may be used for the estimation of off-rate mutations to any residue type and also multi-point mutations. A number of machine learning models are built from a combination of molecular and hotspot descriptors, with the best models achieving a Pearson's Correlation Coefficient of 0.79 with experimental off-rates and a Matthew's Correlation Coefficient of 0.6 in the detection of rare stabilizing mutations. Using specialized feature selection models we identify descriptors that are highly specific and, conversely, broadly important to predicting the effects of different classes of mutations, interface regions and complexes. Our results also indicate that the distribution of the critical stability regions across protein-protein interfaces is a function of complex size more strongly than interface area. In addition, mutations at the rim are critical for the stability of small complexes, but consistently harder to characterize. The relationship between hotregion size and the dissociation rate is also investigated and, using hotspot descriptors which model cooperative effects within hotregions, we show how the

Nanomolar concentration of blood-soluble drag-reducing polymer inhibits experimental metastasis of human breast cancer cells

PubMed Central

Ding, Zhijie; Joy, Marion; Kameneva, Marina V; Roy, Partha

2017-01-01

Metastasis is the leading cause of cancer mortality. Extravasation of cancer cells is a critical step of metastasis. We report a novel proof-of-concept study that investigated whether non-toxic blood-soluble chemical agents capable of rheological modification of the near-vessel-wall blood flow can reduce extravasation of tumor cells and subsequent development of metastasis. Using an experimental metastasis model, we demonstrated that systemic administration of nanomolar concentrations of so-called drag-reducing polymer dramatically impeded extravasation and development of pulmonary metastasis of breast cancer cells in mice. This is the first proof-of-principle study to directly demonstrate physical/rheological, as opposed to chemical, way to prevent cancer cells from extravasation and developing metastasis and, thus, it opens the possibility of a new direction of adjuvant interventional approach in cancer. PMID:28280386

Dissociative complexity: Antecedents and clinical correlates of a new construct.

PubMed

Briere, John; Dietrich, Anne; Semple, Randye J

2016-09-01

To the extent that dissociation is a multidimensional phenomenon, and given a growing literature on complex posttraumatic outcomes, we hypothesized a new construct: dissociative complexity (DC). DC is defined as the tendency to simultaneously endorse multiple, relatively independent dissociative dimensions into their clinical ranges, and therefore represents the overall breadth or complexity of an individual's dissociative response. DC was evaluated in general population and prison participants using the Multiscale Dissociation Inventory (MDI; Briere, 2002). DC was higher among prisoners and women, and, as hypothesized, was associated with cumulative trauma and serious comorbidities (suicidality and substance abuse), even when controlling for generally elevated dissociation. DC appears to be a meaningful clinical construct that is phenomenologically and empirically different from a unidimensional index of dissociative severity. DC may serve as a clinical marker for multiple trauma exposures, complex dissociative outcomes, and risk of problematic comorbidities. (PsycINFO Database Record (c) 2016 APA, all rights reserved).

Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

DOE Office of Scientific and Technical Information (OSTI.GOV)

B. J. Mincher; S. K. Cole; W. J. Cooper

2007-02-01

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance ofmore » the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.« less

Trauma-Related Dissociation Is Linked With Maladaptive Personality Functioning

PubMed Central

Granieri, Antonella; Guglielmucci, Fanny; Costanzo, Antonino; Caretti, Vincenzo; Schimmenti, Adriano

2018-01-01

Background: Extensive research has demonstrated the positive associations among the exposure to traumatic experiences, the levels of dissociation, and the severity of psychiatric symptoms in adults. However, it has been hypothesized in clinical literature that an excessive activation of the dissociative processes following multiple traumatic experiences may jeopardize the psychological and behavioral functioning of the individuals, fostering higher levels of maladaptive personality functioning. Methods: The study involved 322 adult volunteers from Italy. Participants completed measures on traumatic experiences, dissociation, and maladaptive personality traits. Results: The number of traumatic experiences reported by participants were positively associated with dissociation scores and maladaptive personality scores. Mediation analyses showed that dissociation acted as a partial mediator in the relationship between traumatic experiences and overall maladaptive personality functioning. Regression curve analyses showed that the positive association between maladaptive personality functioning and dissociation was stronger among participants with higher exposure to traumatic experiences. Conclusion: Exposure to multiple traumatic experiences may increase the risk for an excessive activation of the dissociative processes, which in turn may generate severe impairments in multiple domains of personality functioning. PMID:29887807

Dissociative disorders in acute psychiatric inpatients in Taiwan.

PubMed

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

2017-04-01

Dissociative disorders have been documented to be common psychiatric disorders which can be detected reliably with standardized diagnostic instruments in North American and European psychiatric inpatients and outpatients (20.6% and 18.4%, respectively). However, there are concerns about their cross-cultural manifestations as an apparently low prevalence rate has been reported in East Asian inpatients and outpatients (1.7% and 4.9%, respectively). It is unknown whether the clinical profile of dissociative disorders in terms of their core symptomatic clusters, associated comorbid disorders, and environmental risk factors that has emerged in western clinical populations can also be found in non-western clinical populations. A standardized structured interview for DSM-IV dissociative disorders, post-traumatic stress disorder, and a history of interpersonal victimization was administered in a sample of Taiwanese acute psychiatric inpatients. Our results showed that 19.5% of our participants met criteria for a DSM-IV dissociative disorder, mostly dissociative disorder not otherwise specified. More importantly, the western clinical profile of dissociative disorders also characterized our patients, including a poly-symptomatic presentation and a history of interpersonal trauma in both childhood and adulthood. Our results lend support to the conclusion that cross-cultural manifestations of dissociative pathology in East Asia are similar to those in North America and Europe. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.

Dissociation in trauma: a new definition and comparison with previous formulations.

PubMed

Nijenhuis, Ellert R S; van der Hart, Onno

2011-01-01

Amid controversy regarding the psychobiological construct of dissociation, efforts to formulate a precise definition of dissociation are rare. Some understandings of dissociation are so broad that a host of common psychobiological phenomena would qualify as dissociative. Overly narrow conceptualizations of dissociation exclude phenomena that originally, and for good reasons, have been regarded as dissociative. A common lack of conceptual distinctions between dissociation as process, organization, deficit, psychological defense, and symptom adds to the current confusion. In previous publications, we criticized many of these perspectives and proposed a detailed psychobiological theory of dissociation in trauma. However, what has remained missing is a precise definition of dissociation in trauma. This article first presents such a definition and elucidates its various components. Next the new definition is compared with several other major definitions of the concept. The strengths of the new formulation are highlighted and discussed.

Somatization as a predictor of suicidal ideation in dissociative disorders.

PubMed

Oztürk, Erdinç; Sar, Vedat

2008-12-01

This study was concerned with correlates of suicidal ideation among patients with chronic complex dissociative disorders. Participants were 40 patients diagnosed as having either dissociative identity disorder or dissociative disorder not otherwise specified according to the DSM-IV. The Dissociative Disorders Interview Schedule, the Dissociative Experiences Scale, the Somatoform Dissociation and the Childhood Trauma Questionnaires, the Spielberger Trait Anger Inventory, the Beck Suicidal Ideation Scale, and the Borderline Personality Disorder section of the Structured Clinical Interview for DSM-IV Personality Disorders were administered to all patients. Patients with suicidal ideas (n = 15) had concurrent somatization disorder more frequently than the remaining patients. Having significantly high scores on both trait and state dissociation measures, their dissociative disorder was more severe than that of the patients with no suicidal ideation. They had elevated scores for childhood emotional abuse, physical abuse and emotional neglect. Concurrent somatization disorder diagnosis was the only predictor of suicidal ideation when childhood trauma scores and borderline personality disorder diagnosis were controlled. Among dissociative patients, there is an association between somatization and suicidal ideation. A trauma-related insecure attachment pattern is considered as a common basis of this symptom cluster.

Cognitive processes in dissociation: an analysis of core theoretical assumptions.

PubMed

Giesbrecht, Timo; Lynn, Steven Jay; Lilienfeld, Scott O; Merckelbach, Harald

2008-09-01

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 performance (e.g., heightened distractibility). Some of the cognitive phenomena (e.g., weakened cognitive inhibition) associated with dissociation appear to be dependent on the emotional or attentional context. Contrary to a widespread assumption in the clinical literature, dissociation does not appear to be related to avoidant information processing. Rather, it is associated with an enhanced propensity toward pseudo-memories, possibly mediated by heightened levels of interrogative suggestibility, fantasy proneness, and cognitive failures. Evidence for a link between dissociation and either memory fragmentation or early trauma based on objective measures is conspicuously lacking. The authors identify a variety of methodological issues and discrepancies that make it difficult to articulate a comprehensive framework for cognitive mechanisms in dissociation. The authors conclude with a discussion of research domains (e.g., sleep-related experiences, drug-related dissociation) that promise to advance our understanding of cognition and dissociation.

Case report: Improvement in dissociative symptoms with mixed amphetamine salts.

PubMed

Scarella, Timothy M; Franzen, Jamie R

2017-01-01

Symptoms of dissociation, including dissociative amnesia, depersonalization, and derealization, commonly develop in individuals subject to chronic and repeated trauma during development. This includes the trauma of environmental inability to facilitate development of adequate cognitive strategies for coping with strong negative emotions. Dissociation likely involves dysregulated balance of prefrontal inhibition of limbic structures and inadequate regulation of attentional bias by both prefrontal and limbic systems. There is currently no established psychopharmacologic treatment for dissociative symptoms. Here the case of a woman with severe dissociative symptoms that were markedly improved with the administration of mixed amphetamine salts is discussed. Potential neurobiologic mechanisms for dissociative symptom improvement with psychostimulants are discussed.

Activation energies for dissociation of double strand oligonucleotide anions: evidence for watson-crick base pairing in vacuo.

PubMed

Schnier, P D; Klassen, J S; Strittmatter, E F; Williams, E R

1998-09-23

The dissociation kinetics of a series of complementary and noncomplementary DNA duplexes, (TGCA)(2) (3-), (CCGG)(2) (3-), (AATTAAT)(2) (3-), (CCGGCCG)(2) (3-), A(7)*T(7) (3-), A(7)*A(7) (3-), T(7)*T(7) (3-), and A(7)*C(7) (3-) were investigated using blackbody infrared radiative dissociation in a Fourier transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Activation energies range from 1.2 to 1.7 eV, and preexponential factors range from 10(13) to 10(19) s(-1). Dissociation of the duplexes results in cleavage of the noncovalent bonds and/or cleavage of covalent bonds leading to loss of a neutral nucleobase followed by backbone cleavage producing sequence-specific (a - base) and w ions. Four pieces of evidence are presented which indicate that Watson-Crick (WC) base pairing is preserved in complementary DNA duplexes in the gas phase: i. the activation energy for dissociation of the complementary dimer, A(7)*T(7) (3-), to the single strands is significantly higher than that for the related noncomplementary A(7)*A(7) (3-) and T(7)*T(7) (3-) dimers, indicating a stronger interaction between strands with a specific base sequence, ii. extensive loss of neutral adenine occurs for A(7)*A(7) (3-) and A(7)*C(7) (3-) but not for A(7)*T(7) (3-) consistent with this process being shut down by WC hydrogen bonding, iii. a correlation is observed between the measured activation energy for dissociation to single strands and the dimerization enthalpy (-DeltaH(d)) in solution, and iv. molecular dynamics carried out at 300 and 400 K indicate that WC base pairing is preserved for A(7)*T(7) (3-) duplex, although the helical structure is essentially lost. In combination, these results provide strong evidence that WC base pairing can exist in the complete absence of solvent.

Activation Energies for Dissociation of Double Strand Oligonucleotide Anions: Evidence for Watson–Crick Base Pairing in Vacuo

PubMed Central

Schnier, Paul D.; Klassen, John S.; Strittmatter, Eric F.; Williams*, Evan R.

2005-01-01

The dissociation kinetics of a series of complementary and noncomplementary DNA duplexes, (TGCA)23−, (CCGG)23−, (AATTAAT)23−, (CCGGCCG)23−, A7·T73−, A7·A73−, T7·T73−, and A7·C73− were investigated using blackbody infrared radiative dissociation in a Fourier transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Activation energies range from 1.2 to 1.7 eV, and preexponential factors range from 1013 to 1019 s−1. Dissociation of the duplexes results in cleavage of the noncovalent bonds and/or cleavage of covalent bonds leading to loss of a neutral nucleobase followed by backbone cleavage producing sequence-specific (a – base) and w ions. Four pieces of evidence are presented which indicate that Watson–Crick (WC) base pairing is preserved in complementary DNA duplexes in the gas phase: i. the activation energy for dissociation of the complementary dimer, A7·T73−, to the single strands is significantly higher than that for the related noncomplementary A7·A73− and T7·T73− dimers, indicating a stronger interaction between strands with a specific base sequence, ii. extensive loss of neutral adenine occurs for A7·A73− and A7·C73− but not for A7·T73− consistent with this process being shut down by WC hydrogen bonding, iii. a correlation is observed between the measured activation energy for dissociation to single strands and the dimerization enthalpy (−ΔHd) in solution, and iv. molecular dynamics carried out at 300 and 400 K indicate that WC base pairing is preserved for A7·T73− duplex, although the helical structure is essentially lost. In combination, these results provide strong evidence that WC base pairing can exist in the complete absence of solvent. PMID:16498487

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.

The Contribution of Art Therapy to the Dissociative Disorders.

ERIC Educational Resources Information Center

Murphy, Patricia S.

1994-01-01

Explored concepts of brain hemispheric lateralization and distinct right brain functioning in extensive dissociation by administering Dissociative Experiences Scale to 114 engineering students and 92 university drawing students. Chi-square calculation found differences in dissociative scoring levels between groups that approached significance at…

The tryptophan-derived endogenous arylhydrocarbon receptor ligand 6-formylindolo[3,2-b]carbazole (FICZ) is a nanomolar UVA-photosensitizer in epidermal keratinocytes

PubMed Central

Williams, Joshua D.; Cabello, Christopher M.; Qiao, Shuxi; Wondrak, Georg T.

2014-01-01

Endogenous UVA-chromophores may act as sensitizers of oxidative stress underlying cutaneous photoaging and photocarcinogenesis, but the molecular identity of non-DNA key chromophores displaying UVA-driven photodyamic activity in human skin remains largely undefined. Here we report that 6-formylindolo[3,2-b]carbazole (FICZ), a tryptophan photoproduct and endogenous high affinity aryl hydrocarbon receptor (AhR) agonist, acts as a nanomolar photosensitizer potentiating UVA-induced oxidative stress irrespective of AhR ligand activity. In human HaCaT and primary epidermal keratinocytes, photodynamic induction of apoptosis was elicited by the combined action of solar simulated UVA and FICZ, whereas exposure to the isolated action of UVA or FICZ did not impair viability. In a human epidermal tissue reconstruct, FICZ/UVA-cotreatment caused pronounced phototoxicity inducing keratinocyte cell death, and FICZ photodynamic activity was also substantiated in a murine skin exposure model. Array analysis revealed pronounced potentiation of cellular heat shock, ER stress, and oxidative stress response gene expression observed only upon FICZ/UVA-cotreatment. FICZ photosensitization caused intracellular oxidative stress, and comet analysis revealed introduction of formamidopyrimidine-DNA glycosylase (FPG)-sensitive oxidative DNA lesions suppressible by antioxidant cotreatment. Taken together, our data demonstrate that the endogenous AhR ligand FICZ displays nanomolar photodynamic activity representing a molecular mechanism of UVA-induced photooxidative stress potentially operative in human skin. PMID:25431849

[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.

Dissociation From a Cross-Cultural Perspective: Implications of Studies in Brazil.

PubMed

Maraldi, Everton de Oliveira; Krippner, Stanley; Barros, Maria Cristina Monteiro; Cunha, Alexandre

2017-07-01

A major issue in the study of dissociation concerns the cross-cultural validity of definitions and measurements used to identify and classify dissociative disorders. There is also extensive debate on the etiological factors underlying dissociative experiences. Cross-cultural research is essential to elucidate these issues, particularly regarding evidence obtained from countries in which the study of dissociation is still in its infancy. The aim of this article was to discuss Brazilian research on the topic of dissociation, highlighting its contributions for the understanding of dissociative experiences in nonclinical populations and for the validity and relevance of dissociative disorders in the contexts of psychiatry, psychology, and psychotherapy. We also consider the ways in which dissociative experiences are assimilated by Brazilian culture and religious expressions, and the implications of Brazilian studies for the sociocultural investigation of dissociation. We conclude by addressing the limitations of these studies and potential areas for future research.

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

Investigating peri-traumatic dissociation using hypnosis during a traumatic film.

PubMed

Holmes, Emily A; Oakley, David A; Stuart, Aailsa D P; Brewin, Chris R

2006-01-01

We investigated the hypothesis that inducing a dissociative response (detachment) in healthy volunteers while they were watching a trauma film would lead to increased numbers of intrusive memories of the film during the following week. Hypnotized participants were given suggestions to dissociate during part of the film, and to watch the rest of the film normally from their own perspective. The order of these conditions, and the section of film watched under the two conditions, were counterbalanced. As predicted, watching the film under both conditions led to increases in dissociation. Explicit suggestions to dissociate were generally effective in inducing higher levels of dissociation. Contrary to prediction, there were no more intrusive memories of sections of the film for which participants had received dissociation suggestions. Implications of our results for views of the relationship between peri-traumatic dissociation and intrusive memories are discussed.

Cognitive processes in dissociation: comment on Giesbrecht et al. (2008).

PubMed

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 have challenged the widely accepted trauma theory of dissociation, which holds that dissociative symptoms are caused by traumatic stress. In doing so, the authors have outlined 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 Giesbrecht et al.'s argument that there is no relationship between trauma and dissociation.

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

Dissociations between developmental dyslexias and attention deficits.

PubMed

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

Dissociative phenomena in congenital monocular elevation deficiency.

PubMed

Olson, R J; Scott, W E

1998-04-01

Monocular elevation deficiency is characterized by unilateral limitation of elevation in both adduction and abduction and is usually present at birth. Dissociative phenomena such as dissociated vertical deviation are well recognized in association with conditions such as congenital esotropia but much less so in association with conditions such as congenital monocular elevation deficiency. All 129 patients given the diagnosis of monocular elevation deficiency or double elevator palsy in the Pediatric Ophthalmology and Strabismus Clinic at the University of Iowa Hospitals and Clinics between 1971 and 1995 were reviewed. After those with history of trauma, myasthenia gravis, thyroid eye disease, orbital lesions, Brown syndrome, or monocular elevation deficiency with acquired onset were excluded, 31 patients with congenital monocular elevation deficiency remained for retrospective study. First diagnosed at median age 2.6 years (although all were noted by parents at less than 6 months of age) with mean follow-up of 5.0 years (up to 15.5 years), 9 of 31 (29%) developed dissociated vertical deviation in the eye with monocular elevation deficiency, all of whom had undergone strabismus surgery 0 to 9.7 years previously (mean 3.5 years). Those who developed dissociated vertical deviation were generally younger, were followed up longer, and had more accompanying horizontal strabismus than did those who did not develop dissociated vertical deviation. The results did not reach significance. The current study demonstrates that dissociated vertical deviation occurs in association with monocular elevation deficiency.

Dissociative photoionization of isoprene: experiments and calculations.

PubMed

Liu, Xianyun; Zhang, Weijun; Wang, Zhenya; Huang, Mingqiang; Yang, Xibin; Tao, Ling; Sun, Yue; Xu, Yuntao; Shan, Xiaobin; Liu, Fuyi; Sheng, Liusi

2009-03-01

Vacuum ultraviolet (VUV) dissociative photoionization of isoprene in the energy region 8.5-18 eV was investigated with photoionization mass spectroscopy (PIMS) using synchrotron radiation (SR). The ionization energy (IE) of isoprene as well as the appearance energies (AEs) of its fragment ions C(5)H(7) (+), C(5)H(5) (+), C(4)H(5) (+), C(3)H(6) (+), C(3)H(5) (+), C(3)H(4) (+), C(3)H(3) (+) and C(2)H(3) (+) were determined with photoionization efficiency (PIE) curves. The dissociation energies of some possible dissociation channels to produce those fragment ions were also determined experimentally. The total energies of C(5)H(8) and its main fragments were calculated using the Gaussian 03 program and the Gaussian-2 method. The IE of C(5)H(8), the AEs for its fragment ions, and the dissociation energies to produce them were predicted using the high-accuracy energy model. According to our results, the experimental dissociation energies were in reasonable agreement with the calculated values of the proposed photodissociation channels of C(5)H(8). Copyright (c) 2009 John Wiley & Sons, Ltd.

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.

Quantitative theory of electroosmotic flow in fused-silica capillaries using an extended site-dissociation--site-binding model.

PubMed

Zhou, Marilyn X; Foley, Joe P

2006-03-15

To optimize separations in capillary electrophoresis, it is important to control the electroosmotic mobility of the running buffer and the factors that affect it. Through the application of a site-dissociation-site-binding model, we demonstrated that the electroosmotic mobility could be controlled qualitatively and quantitatively by the parameters related to the physical and chemical properties of the running buffer: pH, cation valence, ionic strength, viscosity, activity, and dissociation constant. Our study illustrated that the logarithm of the number of apparent silanol sites on a fused-silica surface has a linear relationship with the pH of a buffer solution. The extension of the chemical kinetics approach allowed us to obtain the thickness of the electrical double layer when multivalent inorganic cations are present with monovalent cations in a buffer solution, and we found that the thickness of the electrical double layer does not depend on the charge of anions. The general equation to predict the electroosmotic mobility suggested here also indicates the increase of electroosmotic mobility with temperature. The general equation was experimentally verified by three buffer scenarios: (i) buffers containing only monovalent cations; (ii) buffers containing multivalent inorganic cations; and (iii) buffers containing cations and neutral additives. The general equation can explain the experimental observations of (i) a maximum electroosmotic mobility for the first scenario as the pH was varied at constant ionic strength and (ii) the inversion and maximum value of the electroosmotic mobility for the second scenario when the concentration of divalent cations was varied at constant pH. A good agreement between theory and experiment was obtained for each scenario.

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.

The DSM-5 dissociative-PTSD subtype: can levels of depression, anxiety, hostility, and sleeping difficulties differentiate between dissociative-PTSD and PTSD in rape and sexual assault victims?

PubMed

Armour, Cherie; Elklit, Ask; Lauterbach, Dean; Elhai, Jon D

2014-05-01

The DSM-5 currently includes a dissociative-PTSD subtype within its nomenclature. Several studies have confirmed the dissociative-PTSD subtype in both American Veteran and American civilian samples. Studies have begun to assess specific factors which differentiate between dissociative vs. non-dissociative PTSD. The current study takes a novel approach to investigating the presence of a dissociative-PTSD subtype in its use of European victims of sexual assault and rape (N=351). Utilizing Latent Profile Analyses, we hypothesized that a discrete group of individuals would represent a dissociative-PTSD subtype. We additionally hypothesized that levels of depression, anger, hostility, and sleeping difficulties would differentiate dissociative-PTSD from a similarly severe form of PTSD in the absence of dissociation. Results concluded that there were four discrete groups termed baseline, moderate PTSD, high PTSD, and dissociative-PTSD. The dissociative-PTSD group encompassed 13.1% of the sample and evidenced significantly higher mean scores on measures of depression, anxiety, hostility, and sleeping difficulties. Implications are discussed in relation to both treatment planning and the newly published DSM-5. Copyright © 2014 Elsevier Ltd. All rights reserved.

Infrared laser dissociation of single megadalton polymer ions in a gated electrostatic ion trap: the added value of statistical analysis of individual events.

PubMed

Halim, Mohammad A; Clavier, Christian; Dagany, Xavier; Kerleroux, Michel; Dugourd, Philippe; Dunbar, Robert C; Antoine, Rodolphe

2018-05-07

In this study, we report the unimolecular dissociation mechanism of megadalton SO 3 -containing poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polymer cations and anions with the aid of infrared multiphoton dissociation coupled to charge detection ion trap mass spectrometry. A gated electrostatic ion trap ("Benner trap") is used to store and detect single gaseous polymer ions generated by positive and negative polarity in an electrospray ionization source. The trapped ions are then fragmented due to the sequential absorption of multiple infrared photons produced from a continuous-wave CO 2 laser. Several fragmentation pathways having distinct signatures are observed. Highly charged parent ions characteristically adopt a distinctive "stair-case" pattern (assigned to the "fission" process) whereas low charge species take on a "funnel like" shape (assigned to the "evaporation" process). Also, the log-log plot of the dissociation rate constants as a function of laser intensity between PAMPS positive and negative ions is significantly different.

Stripping analysis of nanomolar perchlorate in drinking water with a voltammetric ion-selective electrode based on thin-layer liquid membrane.

PubMed

Kim, Yushin; Amemiya, Shigeru

2008-08-01

A highly sensitive analytical method is required for the assessment of nanomolar perchlorate contamination in drinking water as an emerging environmental problem. We developed the novel approach based on a voltammetric ion-selective electrode to enable the electrochemical detection of "redox-inactive" perchlorate at a nanomolar level without its electrolysis. The perchlorate-selective electrode is based on the submicrometer-thick plasticized poly(vinyl chloride) membrane spin-coated on the poly(3-octylthiophene)-modified gold electrode. The liquid membrane serves as the first thin-layer cell for ion-transfer stripping voltammetry to give low detection limits of 0.2-0.5 nM perchlorate in deionized water, commercial bottled water, and tap water under a rotating electrode configuration. The detection limits are not only much lower than the action limit (approximately 246 nM) set by the U.S. Environmental Protection Agency but also are comparable to the detection limits of the most sensitive analytical methods for detecting perchlorate, that is, ion chromatography coupled with a suppressed conductivity detector (0.55 nM) or electrospray ionization mass spectrometry (0.20-0.25 nM). The mass transfer of perchlorate in the thin-layer liquid membrane and aqueous sample as well as its transfer at the interface between the two phases were studied experimentally and theoretically to achieve the low detection limits. The advantages of ion-transfer stripping voltammetry with a thin-layer liquid membrane against traditional ion-selective potentiometry are demonstrated in terms of a detection limit, a response time, and selectivity.

Dissociation: adjustment or distress? Dissociative phenomena, absorption and quality of life among Israeli women who practice channeling compared to women with similar traumatic history.

PubMed

Stolovy, Tali; Lev-Wiesel, Rachel; Witztum, Eliezer

2015-06-01

This study aimed to explore the relationship between traumatic history, dissociative phenomena, absorption and quality of life among a population of channelers, in comparison with a population of non-channelers with similar traumatic history. The study sample included 150 women. The measures included Traumatic Experiences Scale, Dissociative Experience Scale, Absorption Scale, Brief Symptom Inventory and Quality of Life (QOL) Assessment. Channelers presented significantly higher levels of dissociation, absorption and psychological health compared to the other group. Dissociation and absorption were trauma-related only among the comparison group. Hence, dissociation has different qualities among different people, and spiritual practice contributes to QOL.

Dissociative Experience and Cultural Neuroscience: Narrative, Metaphor and Mechanism

PubMed Central

Kirmayer, Laurence J.

2016-01-01

Approaches to trance and possession in anthropology have tended to use outmoded models drawn from psychodynamic theory or treated such dissociative phenomena as purely discursive processes of attributing action and experience to agencies other than the self. Within psychology and psychiatry, understanding of dissociative disorders has been hindered by polemical “either/or” arguments: either dissociative disorders are real, spontaneous alterations in brain states that reflect basic neurobiological phenomena, or they are imaginary, socially constructed role performances dictated by interpersonal expectations, power dynamics and cultural scripts. In this paper, we outline an approach to dissociative phenomena, including trance, possession and spiritual and healing practices, that integrates the neuropsychological notions of underlying mechanism with sociocultural processes of the narrative construction and social presentation of the self. This integrative model, grounded in a cultural neuroscience, can advance ethnographic studies of dissociation and inform clinical approaches to dissociation through careful consideration of the impact of social context. PMID:18213511

Dissociative experience and cultural neuroscience: narrative, metaphor and mechanism.

PubMed

Seligman, Rebecca; Kirmayer, Laurence J

2008-03-01

Approaches to trance and possession in anthropology have tended to use outmoded models drawn from psychodynamic theory or treated such dissociative phenomena as purely discursive processes of attributing action and experience to agencies other than the self. Within psychology and psychiatry, understanding of dissociative disorders has been hindered by polemical "either/or" arguments: either dissociative disorders are real, spontaneous alterations in brain states that reflect basic neurobiological phenomena, or they are imaginary, socially constructed role performances dictated by interpersonal expectations, power dynamics and cultural scripts. In this paper, we outline an approach to dissociative phenomena, including trance, possession and spiritual and healing practices, that integrates the neuropsychological notions of underlying mechanism with sociocultural processes of the narrative construction and social presentation of the self. This integrative model, grounded in a cultural neuroscience, can advance ethnographic studies of dissociation and inform clinical approaches to dissociation through careful consideration of the impact of social context.

Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)5 via a singlet pathway upon excitation at 266 nm

PubMed Central

Leitner, T.; Mazza, T.; Schröder, H.; Kunnus, K.; Schreck, S.; Radcliffe, P.; Düsterer, S.; Meyer, M.; Föhlisch, A.

2017-01-01

We prove the hitherto hypothesized sequential dissociation of Fe(CO)5 in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)4 within the temporal resolution of the experiment and further to Fe(CO)3 within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)5, Fe(CO)4, and Fe(CO)3 showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)5 complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes. PMID:28595420

Co-occurrence of dissociative identity disorder and borderline personality disorder.

PubMed

Ross, Colin A; Ferrell, Lynn; Schroeder, Elizabeth

2014-01-01

The literature indicates that, among individuals with borderline personality disorder, pathological dissociation correlates with a wide range of impairments and difficulties in psychological function. It also predicts a poorer response to dialectical behavior therapy for borderline personality disorder. We hypothesized that (a) dissociative identity disorder commonly co-occurs with borderline personality disorder and vice versa, and (b) individuals who meet criteria for both disorders have more comorbidity and trauma than individuals who meet criteria for only 1 disorder. We interviewed a sample of inpatients in a hospital trauma program using 3 measures of dissociation. The most symptomatic group was those participants who met criteria for both borderline personality disorder and dissociative identity disorder on the Dissociative Disorders Interview Schedule, followed by those who met criteria for dissociative identity disorder only, then those with borderline personality disorder only, and finally those with neither disorder. Greater attention should be paid to the relationship between borderline personality disorder and dissociative identity disorder.

Development, Reliability, and Validity of a Child Dissociation Scale.

ERIC Educational Resources Information Center

Putnam, Frank W.; And Others

1993-01-01

Evaluation of the Child Dissociative Checklist found it to be a reliable and valid observer report measure of dissociation in children, including sexually abused girls and children with dissociative disorder and with multiple personality disorder. The checklist, which is appended, is intended as a clinical screening instrument and research measure…

Lost in dissociation: The main paradigms in unconscious cognition.

PubMed

Augusto, Luis M

2016-05-01

Contemporary studies in unconscious cognition are essentially founded on dissociation, i.e., on how it dissociates with respect to conscious mental processes and representations. This is claimed to be in so many and diverse ways that one is often lost in dissociation. In order to reduce this state of confusion we here carry out two major tasks: based on the central distinction between cognitive processes and representations, we identify and isolate the main dissociation paradigms; we then critically analyze their key tenets and reported findings. Copyright © 2016 Elsevier Inc. All rights reserved.

Sleep loss increases dissociation and affects memory for emotional stimuli.

PubMed

van Heugten-van der Kloet, Dalena; Giesbrecht, Timo; Merckelbach, Harald

2015-06-01

Because of their dreamlike character, authors have speculated about the role that the sleep-wake cycle plays in dissociative symptoms. We investigated whether sleep loss fuels dissociative symptoms and undermines cognitive efficiency, particularly memory functioning. Fifty-six healthy undergraduate students were randomly assigned to an experimental group (n = 28) and a control group (n = 28). The experimental group was deprived of sleep for 36 h in a sleep laboratory; the control group had a regular night of sleep. Sleepiness, mood, and dissociative symptoms were assessed 6 times in the experimental group (control group: 4 times). Several cognitive tasks were administered. Sleep deprivation led to an increase in dissociative symptoms, which was mediated by levels of general distress. Feelings of sleepiness preceded an increase of dissociative symptoms and deterioration of mood. Finally, sleep loss also undermined memory of emotional material, especially in highly dissociative individuals. Limitations included moderate reliability of the mood scale, limited generalizability due to student sample, and a relatively short period of intensive sleep deprivation rather than lengthy but intermittent sleep loss, representative of a clinical population. We found that sleep deprivation had significant effects on dissociation, sleepiness, and mood. Specifically, sleepiness and dissociation increased during the night, while mood deteriorated. Our findings stress the importance of sleep deficiencies in the development of dissociative symptoms. They support the view that sleep disruptions fuel distress, but also degrade memory and attentional control. It is against this background that dissociative symptoms may arise. Copyright © 2014 Elsevier Ltd. All rights reserved.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy.

PubMed

Chatterley, Adam S; Lackner, Florian; Neumark, Daniel M; Leone, Stephen R; Gessner, Oliver

2016-06-07

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10(13) and 2.2 × 10(14) W cm(-2). The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br(++). However, the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br(+), and Br(++), respectively. Transient molecular ion features assigned to DBE(+) and DBE(++) are observed, with dynamics linked to the production of Br(+) products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE(+) ions on a shallow potential energy surface. The appearance of Br(+) ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE(+) ionic species. Dicationic Br(++) products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy

DOE PAGES

Chatterley, Adam S.; Lackner, Florian; Neumark, Daniel M.; ...

2016-05-11

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10 13 and 2.2 × 10 14 W cm -2. The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br ++. However,more » the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br +, and Br ++, respectively. Transient molecular ion features assigned to DBE + and DBE ++ are observed, with dynamics linked to the production of Br + products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE + ions on a shallow potential energy surface. The appearance of Br + ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE + ionic species. Dicationic Br ++ products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.« less

Theoretical Electric Dipole Moments and Dissociation Energies for the Ground States of GaH-BrH

NASA Technical Reports Server (NTRS)

Pettersson, Lars G. M.; Langhoff, Stephen R.

1986-01-01

Reliable experimental diople moments are available for the ground states of SeH and BrH whereas no values have been reported for GaH and AsH a recently reported experimental dipole moment for GeH of 1.24 + or -0.01 D has been seriously questioned, and a much lower value of, 0.1 + or - 0.05 D, suggested. In this work, we report accurate theoretical dipole moments, dipole derivatives, dissociation energies, and spectroscopic constants (tau(sub e), omega(sub e)) for the ground states of GaH through BrH.

Method for accurate determination of dissociation constants of optical ratiometric systems: chemical probes, genetically encoded sensors, and interacting molecules.

PubMed

Pomorski, Adam; Kochańczyk, Tomasz; Miłoch, Anna; Krężel, Artur

2013-12-03

Ratiometric chemical probes and genetically encoded sensors are of high interest for both analytical chemists and molecular biologists. Their high sensitivity toward the target ligand and ability to obtain quantitative results without a known sensor concentration have made them a very useful tool in both in vitro and in vivo assays. Although ratiometric sensors are widely used in many applications, their successful and accurate usage depends on how they are characterized in terms of sensing target molecules. The most important feature of probes and sensors besides their optical parameters is an affinity constant toward analyzed molecules. The literature shows that different analytical approaches are used to determine the stability constants, with the ratio approach being most popular. However, oversimplification and lack of attention to detail results in inaccurate determination of stability constants, which in turn affects the results obtained using these sensors. Here, we present a new method where ratio signal is calibrated for borderline values of intensities of both wavelengths, instead of borderline ratio values that generate errors in many studies. At the same time, the equation takes into account the cooperativity factor or fluorescence artifacts and therefore can be used to characterize systems with various stoichiometries and experimental conditions. Accurate determination of stability constants is demonstrated utilizing four known optical ratiometric probes and sensors, together with a discussion regarding other, currently used methods.

Hippocampal and Amygdalar Volumes in Dissociative Identity Disorder

PubMed Central

Vermetten, Eric; Schmahl, Christian; Lindner, Sanneke; Loewenstein, Richard J.; Bremner, J. Douglas

2011-01-01

Objective Smaller hippocampal volume has been reported in several stress-related psychiatric disorders, including posttraumatic stress disorder (PTSD), borderline personality disorder with early abuse, and depression with early abuse. Patients with borderline personality disorder and early abuse have also been found to have smaller amygdalar volume. The authors examined hippocampal and amygdalar volumes in patients with dissociative identity disorder, a disorder that has been associated with a history of severe childhood trauma. Method The authors used magnetic resonance imaging to measure the volumes of the hippocampus and amygdala in 15 female patients with dissociative identity disorder and 23 female subjects without dissociative identity disorder or any other psychiatric disorder. The volumetric measurements for the two groups were compared. Results Hippocampal volume was 19.2% smaller and amygdalar volume was 31.6% smaller in the patients with dissociative identity disorder, compared to the healthy subjects. The ratio of hippocampal volume to amygdalar volume was significantly different between groups. Conclusions The findings are consistent with the presence of smaller hippocampal and amygdalar volumes in patients with dissociative identity disorder, compared with healthy subjects. PMID:16585437

Hippocampal and amygdalar volumes in dissociative identity disorder.

PubMed

Vermetten, Eric; Schmahl, Christian; Lindner, Sanneke; Loewenstein, Richard J; Bremner, J Douglas

2006-04-01

Smaller hippocampal volume has been reported in several stress-related psychiatric disorders, including posttraumatic stress disorder (PTSD), borderline personality disorder with early abuse, and depression with early abuse. Patients with borderline personality disorder and early abuse have also been found to have smaller amygdalar volume. The authors examined hippocampal and amygdalar volumes in patients with dissociative identity disorder, a disorder that has been associated with a history of severe childhood trauma. The authors used magnetic resonance imaging to measure the volumes of the hippocampus and amygdala in 15 female patients with dissociative identity disorder and 23 female subjects without dissociative identity disorder or any other psychiatric disorder. The volumetric measurements for the two groups were compared. Hippocampal volume was 19.2% smaller and amygdalar volume was 31.6% smaller in the patients with dissociative identity disorder, compared to the healthy subjects. The ratio of hippocampal volume to amygdalar volume was significantly different between groups. The findings are consistent with the presence of smaller hippocampal and amygdalar volumes in patients with dissociative identity disorder, compared with healthy subjects.

Childhood maltreatment and intimate partner violence in dissociative disorder patients.

PubMed

Webermann, Aliya R; Brand, Bethany L; Chasson, Gregory S

2014-01-01

Childhood maltreatment (CM) is a risk factor for subsequent intimate partner violence (IPV) in adulthood, with high rates of retrospectively reported CM among IPV victims and perpetrators. A theorized mechanism of the link between CM and IPV is dissociation. Dissociation may allow perpetrators of violence to remain emotionally distant from their behavior and minimize empathy toward those they victimize, enabling them to commit acts of violence similar to their own experiences. Indeed, elevated rates of dissociation and dissociative disorders (DD) have been found among IPV survivors and perpetrators. In addition, in pilot studies, DD clinicians have reported high levels of violent behavior among DD patients. The present study investigates IPV among DD patients with Dissociative Identity Disorder and Dissociative Disorder Not Otherwise Specified, a group with CM rates of 80-95% and severe dissociative symptoms. DD clinicians reported on rates of CM and IPV among 275 DD patients in outpatient treatment. DD patients also completed a self-report measure of dissociation. Analyses assessed the associations between CM typologies and IPV, as well as trait dissociation and IPV. Physical and emotional child abuse were associated with physical IPV, and childhood witnessing of domestic violence (DV) and childhood neglect were associated with emotional IPV. The present study is the first to provide empirical support for a possible CM to adult IPV developmental trajectory among DD patients. Future research is needed to better understand the link between CM and IPV among those with trauma and DD.

Lifetimes and wave functions of ozone metastable vibrational states near the dissociation limit in a full-symmetry approach

NASA Astrophysics Data System (ADS)

Lapierre, David; Alijah, Alexander; Kochanov, Roman; Kokoouline, Viatcheslav; Tyuterev, Vladimir

2016-10-01

Energies and lifetimes (widths) of vibrational states above the lowest dissociation limit of O163 were determined using a previously developed efficient approach, which combines hyperspherical coordinates and a complex absorbing potential. The calculations are based on a recently computed potential energy surface of ozone determined with a spectroscopic accuracy [Tyuterev et al., J. Chem. Phys. 139, 134307 (2013), 10.1063/1.4821638]. The effect of permutational symmetry on rovibrational dynamics and the density of resonance states in O3 is discussed in detail. Correspondence between quantum numbers appropriate for short- and long-range parts of wave functions of the rovibrational continuum is established. It is shown, by symmetry arguments, that the allowed purely vibrational (J =0 ) levels of O163 and O183, both made of bosons with zero nuclear spin, cannot dissociate on the ground-state potential energy surface. Energies and wave functions of bound states of the ozone isotopologue O163 with rotational angular momentum J =0 and 1 up to the dissociation threshold were also computed. For bound levels, good agreement with experimental energies is found: The rms deviation between observed and calculated vibrational energies is 1 cm-1. Rotational constants were determined and used for a simple identification of vibrational modes of calculated levels.

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.

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.

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

NASA Astrophysics Data System (ADS)

Hari, Yvonne; Leumann, Christian J.; Schürch, Stefan

2017-12-01

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a•/ w or d/ z• ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS3 experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π-π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer. [Figure not available: see fulltext.

Somatoform and psychoform dissociation among women with orgasmic and sexual pain disorders.

PubMed

Farina, Benedetto; Mazzotti, Eva; Pasquini, Paolo; Mantione, Maria Giuseppina

2011-01-01

Since the 20th century, psychogenic female sexual dysfunctions (FSD), like some somatoform and conversion disorders, have been considered an expression of somatoform dissociation. Several studies have reported dissociative symptoms in different somatoform and conversion disorders, but limited data are available on dissociation among patients with FSD. The aim of this study was to assess somatoform and psychoform dissociation among patients with women's orgasmic disorder, dyspareunia, and vaginismus. A battery of self-administered questionnaires (Somatoform Dissociation Questionnaire, Dissociative Experiences Scale, Hospital Anxiety and Depression Scale, Impact of Event Scale-Revised) was given to 200 gynecological outpatients to assess psychoform and somatoform dissociation and their association with FSD. A strong association between somatoform dissociation and FSD was observed (adjusted odds ratio [OR] = 5.39, 95% confidence interval [CI] = 1.15-25.32), the association between somatoform and psychoform dissociation being estimated by an adjusted OR of 4.83 (95% CI = 1.17-19.91). Our results are compatible with the idea that some forms of FSD could be regarded as somatoform dissociative disorders.

Spontaneous and deliberate dissociative states in military personnel: are such states helpful?

PubMed

Morgan, Charles A; Taylor, Marcus K

2013-08-01

This study explored distinctions between spontaneous and deliberate dissociative states in 335 military personnel exposed to stressful survival training. Participants completed the Clinician-Administered Dissociative States Scale (CADSS) after a stressful mock-captivity event. They were also asked to indicate whether the dissociative experiences just happened (i.e., spontaneous), or whether they chose to have them happen (i.e., deliberate); and whether they appraised the dissociative experience as helpful (i.e., facilitative) or hurtful (i.e., debilitative) to their ability to cope with the stressful event. A majority (95.4%) endorsed dissociative states during stress. More than half (57.4%) described dissociative experiences as spontaneous, 13.0% as deliberate, and 29.5% endorsed neither. In Special Forces soldiers only, those who endorsed facilitative dissociation exhibited higher total CADSS scores than those who endorsed debilitative dissociation. Seventy-three percent of spontaneous dissociators described the experience as debilitative to coping with stress; conversely, 76% of deliberate dissociators said these experiences facilitated coping with stress. Individuals with prior trauma exposure tended to appraise dissociative states as more debilitative to coping. This research may enhance the fidelity of studies of dissociation constructs and may offer pivot points for prevention and treatment of stress-related disorders. Published 2013. This article is a US Government work and is in the public domain in the USA.

Childhood emotional abuse, dissociation, and suicidality among patients with drug dependency in Turkey.

PubMed

Tamar-Gurol, Defne; Sar, Vedat; Karadag, Figen; Evren, Cuneyt; Karagoz, Mustafa

2008-10-01

The aim of the present study was to determine the prevalence and correlates of dissociative disorders among patients with drug dependency. The Dissociative Experiences Scale (DES) was used to screen 104 consecutive patients at an addiction treatment center. Thirty-seven patients who had scores >or=30 were compared with 21 patients who scored <10 on the DES. Both groups were then evaluated using the Dissociative Disorders Interview Schedule and the Structured Clinical Interview for Dissociative Disorders (SCID-D). The interviewers were blind to the DES scores. Twenty-seven patients (26.0%) had a dissociative disorder according to the SCID-D. Dissociative patients were younger than the non-dissociative group. History of suicide attempt and/or childhood emotional abuse was significant predictors of a dissociative disorder. The majority (59.3%) of dissociative drug users reported that dissociative experiences had existed prior to substance use. More patients in the dissociative disorder than in the non-dissociative group stopped their treatment prematurely. A considerable proportion of drug users have a dissociative disorder, which may also interfere with treatment process. The relatively young age of this subgroup of patients and frequent reports of childhood emotional abuse underline potential preventive benefits of early intervention among adolescents with developmental trauma history and dissociative psychopathology.

Characteristic constants of 2,2',4'-trihydroxyazobenzene-5-sulfonic acid, a reagent for spectrophotometric analysis

USGS Publications Warehouse

Fletcher, Mary H.

1960-01-01

The dye 2,2',4'-trihydroxyazobenzene-5-sulfonic acid, has shown promise as a reagent for the determination of zirconium. As the literature contains very little information about this dye, basic data pertinent to its use as a reagent were determined. The sulfonic acid group and all three of the hydroxy groups show acidic characteristics. Apparent dissociation constants were determined for the three more labile protons and the approximate order of magnitude for the fourth constant was estimated. Absorption spectra for the different ionization species are given. A curve is also included which shows the fraction of dye in the different ionization forms at acidities from 10.35M hydrochloric acid to pH 11.9. A sixth dye species was found in 1.0 to 8.4M potassium hydroxide solutions, but its nature is unknown.

Childhood maltreatment and intimate partner violence in dissociative disorder patients

PubMed Central

Webermann, Aliya R.; Brand, Bethany L.; Chasson, Gregory S.

2014-01-01

Background Childhood maltreatment (CM) is a risk factor for subsequent intimate partner violence (IPV) in adulthood, with high rates of retrospectively reported CM among IPV victims and perpetrators. A theorized mechanism of the link between CM and IPV is dissociation. Dissociation may allow perpetrators of violence to remain emotionally distant from their behavior and minimize empathy toward those they victimize, enabling them to commit acts of violence similar to their own experiences. Indeed, elevated rates of dissociation and dissociative disorders (DD) have been found among IPV survivors and perpetrators. In addition, in pilot studies, DD clinicians have reported high levels of violent behavior among DD patients. Objective The present study investigates IPV among DD patients with Dissociative Identity Disorder and Dissociative Disorder Not Otherwise Specified, a group with CM rates of 80–95% and severe dissociative symptoms. Methods DD clinicians reported on rates of CM and IPV among 275 DD patients in outpatient treatment. DD patients also completed a self-report measure of dissociation. Analyses assessed the associations between CM typologies and IPV, as well as trait dissociation and IPV. Results Physical and emotional child abuse were associated with physical IPV, and childhood witnessing of domestic violence (DV) and childhood neglect were associated with emotional IPV. Conclusions The present study is the first to provide empirical support for a possible CM to adult IPV developmental trajectory among DD patients. Future research is needed to better understand the link between CM and IPV among those with trauma and DD. PMID:25279109

Dissociative symptoms in individuals with gender dysphoria: is the elevated prevalence real?

PubMed

Colizzi, Marco; Costa, Rosalia; Todarello, Orlando

2015-03-30

This study evaluated dissociative symptomatology, childhood trauma and body uneasiness in 118 individuals with gender dysphoria, also evaluating dissociative symptoms in follow-up assessments after sex reassignment procedures were performed. We used both clinical interviews (Dissociative Disorders Interview Schedule) and self-reported scales (Dissociative Experiences Scale). A dissociative disorder of any kind seemed to be greatly prevalent (29.6%). Moreover, individuals with gender dysphoria had a high prevalence of lifetime major depressive episode (45.8%), suicide attempts (21.2%) and childhood trauma (45.8%), and all these conditions were more frequent in patients who fulfilled diagnostic criteria for any kind of dissociative disorder. Finally, when treated, patients reported lower dissociative symptoms. Results confirmed previous research about distress in gender dysphoria and improved mental health due to sex reassignment procedures. However, it resulted to be difficult to ascertain dissociation in the context of gender dysphoria, because of the similarities between the two conditions and the possible limited application of clinical instruments which do not provide an adequate differential diagnosis. Therefore, because the body uneasiness is common to dissociative experiences and gender dysphoria, the question is whether dissociation is to be seen not as an expression of pathological dissociative experiences but as a genuine feature of gender dysphoria. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Psychiatric comorbidity in patients with conversion disorder and prevalence of dissociative symptoms.

PubMed

Yayla, Sinan; Bakım, Bahadır; Tankaya, Onur; Ozer, Omer Akil; Karamustafalioglu, Oguz; Ertekin, Hulya; Tekin, Atilla

2015-01-01

The 1st objective of the current study was to investigate the frequency and types of dissociative symptoms in patients with conversion disorder (CD). The 2nd objective of the current study was to determine psychiatric comorbidity in patients with and without dissociative symptoms. A total of 54 consecutive consenting patients primarily diagnosed with CD according to Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, Text Revision, criteria who were admitted to the psychiatric emergency outpatient clinic of Sisli Etfal Research and Teaching Hospital (Istanbul, Turkey) were included in the study. The Structured Clinical Interview for DSM-IV Axis I Disorders, Structured Interview for DSM-IV Dissociative Disorders, and Dissociative Experiences Scale were administered. Study groups consisted of 20 patients with a dissociative disorder and 34 patients without a diagnosis of any dissociative disorder. A total of 37% of patients with CD had any dissociative diagnosis. The prevalence of dissociative disorders was as follows: 18.5% dissociative disorder not otherwise specified, 14.8% dissociative amnesia, and 3.7% depersonalization disorder. Significant differences were found between the study groups with respect to comorbidity of bipolar disorder, past hypomania, and current and past posttraumatic stress disorder (ps = .001, .028, .015, and .028, respectively). Overall comorbidity of bipolar disorder was 27.8%. Psychiatric comorbidity was higher and age at onset was earlier among dissociative patients compared to patients without dissociative symptoms. The increased psychiatric comorbidity and early onset of conversion disorder found in patients with dissociative symptoms suggest that these patients may have had a more severe form of conversion disorder.

Dissociative tendencies and individual differences in high hypnotic suggestibility.

PubMed

Terhune, Devin Blair; Cardeña, Etzel; Lindgren, Magnus

2011-03-01

Inconsistencies in the relationship between dissociation and hypnosis may result from heterogeneity among highly suggestible individuals, in particular the existence of distinct highly suggestible subtypes that are of relevance to models of psychopathology and the consequences of trauma. This study contrasted highly suggestible subtypes high or low in dissociation on measures of hypnotic responding, cognitive functioning, and psychopathology. Twenty-one low suggestible (LS), 19 low dissociative highly suggestible (LDHS), and 11 high dissociative highly suggestible (HDHS) participants were administered hypnotic suggestibility scales and completed measures of free recall, working memory capacity, imagery, fantasy-proneness, psychopathology, and exposure to stressful life events. HDHS participants were more responsive to positive and negative hallucination suggestions and experienced greater involuntariness during hypnotic responding. They also exhibited impaired working memory capacity, elevated pathological fantasy and dissociative symptomatology, and a greater incidence of exposure to stressful life events. In contrast, LDHS participants displayed superior object visual imagery. These results provide further evidence for two highly suggestible subtypes: a dissociative subtype characterised by deficits in executive functioning and a predisposition to psychopathology, and a subtype that exhibits superior imagery and no observable deficits in functioning.

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.

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.

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…

Thermodynamic and Kinetics Analysis of Peptides Derived from CapZ, NDR, p53, HDM2, and HDM4 Binding to Human S100B

PubMed Central

Wafer, Lucas N.; Streicher, Werner W.; McCallum, Scott A.; Makhatadze, George I.

2012-01-01

S100B is a member of the S100 subfamily of EF-hand proteins that has been implicated in malignant melanoma and neurodegenerative conditions such as Alzheimer's and Parkinson's disease. Calcium-induced conformational changes expose a hydrophobic binding cleft, facilitating interactions with a wide variety of nuclear, cytoplasmic, and extracellular target proteins. Previously, peptides derived from CapZ, p53, NDR, HDM2 and HDM4 have been shown to interact with S100B in a calcium-dependent manner. However, the thermodynamic and kinetic basis of these interactions remains largely unknown. To gain further insight, these peptides were screened against the S100B protein using isothermal titration calorimetry and nuclear magnetic resonance. All peptides were found to have binding affinities in the low micromolar to nanomolar range. Binding-induced changes in the line shapes of S100B backbone 1H and 15N were monitored to obtain the dissociation constants and the kinetic binding parameters. The large microscopic Kon rate constants observed in this study, Kon ≥1×107 M-1s-1, suggest that S100B utilizes a “fly casting mechanism” in the recognition of these peptide targets. PMID:22913742

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…

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.

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,…

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).

Fable or fact?: did Janet really come to repudiate his dissociation theory?

PubMed

Dorahy, Martin J; van der Hart, Onno

2006-01-01

Commencing in the late 1880s Pierre Janet developed the most complete theory of dissociation of his time. It has been suggested that Janet later repudiated his belief in dissociation theory (e.g., Hacking, 1995). Recently this viewpoint has been cited to support skepticism in dissociative identity disorder and researchers and clinicians of dissociation may be faced with such suggestions to challenge their work. The veracity of whether Janet actually recanted, or even lost interest in his dissociation theory is investigated through an examination of his later writings. Although Janet expanded his theoretical interests well beyond phenomena accounted for by dissociation, there is no evidence to indicate he renounced or lost confidence in his dissociation theory.

[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.

Direct measurement of exciton dissociation energy in polymers

NASA Astrophysics Data System (ADS)

Toušek, J.; Toušková, J.; Chomutová, R.; Paruzel, B.; Pfleger, J.

2017-01-01

Exciton dissociation energy was obtained based on the comparison of thickness of the space charge region estimated from the measurement of capacitance of prepared Schottky diode and from the measurement of photovoltage spectra. While the capacitance measurements provide information about the total width of the space charge region (SCR) the surface photovoltaic effect brings information only about the part of the SCR where electric field is sufficiently high to cause dissociation. For determination of the dissociation energy it is sufficient to find the electric potential in the SCR where the process starts.

Trauma-related pathological dissociation in a case with cerebral palsy.

PubMed

Fung, Hong Wang

2016-01-01

This article provides a case report of a Chinese-Cantonese female with both cerebral palsy and dissociative identity disorder. To my knowledge, this is the first report of a case with dissociative identity disorder from Hong Kong, as well as the first report of a case with both dissociative identity disorder and cerebral palsy in the literature. Large-sample studies should be undertaken in the future to investigate the prevalence of dissociative disorders in a variety of populations in Hong Kong, including individuals with diagnosed brain diseases.

Evaluation of the evidence for the trauma and fantasy models of dissociation.

PubMed

Dalenberg, Constance J; Brand, Bethany L; Gleaves, David H; Dorahy, Martin J; Loewenstein, Richard J; Cardeña, Etzel; Frewen, Paul A; Carlson, Eve B; Spiegel, David

2012-05-01

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 engendering confabulated memories of trauma. We examine data related to a series of 8 contrasting predictions based on the trauma model and the fantasy model of dissociation. In keeping with the trauma model, the relationship between trauma and dissociation was consistent and moderate in strength, and remained significant when objective measures of trauma were used. Dissociation was temporally related to trauma and trauma treatment, and was predictive of trauma history when fantasy proneness was controlled. Dissociation was not reliably associated with suggestibility, nor was there evidence for the fantasy model prediction of greater inaccuracy of recovered memory. Instead, dissociation was positively related to a history of trauma memory recovery and negatively related to the more general measures of narrative cohesion. Research also supports the trauma theory of dissociation as a regulatory response to fear or other extreme emotion with measurable biological correlates. We conclude, on the basis of evidence related to these 8 predictions, that there is strong empirical support for the hypothesis that trauma causes dissociation, and that dissociation remains related to trauma history when fantasy proneness is controlled. We find little support for the hypothesis that the dissociation-trauma relationship is due to fantasy proneness or confabulated memories of trauma. 2012 APA, all rights reserved

PTSD, emotion dysregulation, and dissociative symptoms in a highly traumatized sample

PubMed Central

Powers, Abigail; Cross, Dorthie; Fani, Negar; Bradley, Bekh

2015-01-01

Exposure to multiple traumas has been shown to result in many negative mental health outcomes, including posttraumatic stress disorder (PTSD). Dissociation, which involves disruptions in memory, identity, and perceptions, may be a component of PTSD, particularly among individuals who have experienced childhood trauma. Emotion regulation difficulties are also strongly associated with childhood trauma and emotion dysregulation may be a particularly important factor to consider in the development and maintenance of dissociative symptoms. The goal of the present study was to determine whether emotion dysregulation mediated the relationship between PTSD symptoms and dissociation in a sample of 154 (80% female, 97% African-American) adults recruited from a public, urban hospital. PTSD was measured using the Clinician Administered PTSD Scale, emotion dysregulation was measured using the Difficulties in Emotion Regulation Scale, and dissociation was measured using the Multiscale Dissociation Inventory. A linear regression analysis showed that both PTSD and emotion dysregulation were statistically significant predictors of dissociation even after controlling for trauma exposure. Alexithymia and an inability to use emotion regulation strategies in particular were predictive of dissociation above and beyond other predictor variables. Using bootstrapping techniques, we found that overall emotion dyregulation partially mediated the effect of PTSD symptoms on dissociative symptoms. Our results suggest that emotion dysregulation may be important in understanding the relation between PTSD and dissociative symptoms. Treatment approaches may consider a focus on training in emotional understanding and the development of adaptive regulation strategies as a way to address dissociative symptoms in PTSD patients. PMID:25573648

[Dissociative symptoms in patients with mood and anxiety disorders].

PubMed

Moscariello, Marianna Margherita; Ratti, Flavia; Quartini, Adele; Forcén, Fernando Espí; Munuera, Joaquin Nieto; Bersani, Giuseppe

2010-01-01

The objective of this study was to evaluate the occurrence of dissociative symptoms in outpatients affected by mood or anxiety disorder and their potential implication in general psychopathology and treatment response. The sample was recruited at Italian and Spanish psychiatric outpatient services. The sample consisted in 40 (13 Male, 27 Female) outpatients, 22 Italians (55%) and 18 Spanish (45%). Inclusion criteria were the Axis I diagnosis of any DSM-IV-TR mood or anxiety disorder and Clinical Global Impression/Global Severity Index (CGI) baseline scores > or = 3 and Hamilton Depression Rating Scale (HAM-D) and Hamilton Anxiety Scale (HAM-A) baseline scores > or = 18. General psychopathology, dissociative symptoms and personality traits were respectively assessed by the self-report symptom inventory Symptom Check-List 90 (SCL-90), the Dissociative Experience Scale (DES) and the Cloninger's Temperament and Character Inventory (TCI). Dissociative symptoms emerged as relatively frequent in mood and anxiety disorders. Globally, depression symptoms seem to correlate positively with the dissociative experiences and the severity of global psychopathology. Dissociative symptoms seem to correlate positively with some personality traits and the severity of global psychopathology and should receive further investigation in clinical practice, as might be a predictor of poor response to conventional drug treatment.

Trauma-induced dissociative amnesia in World War I combat soldiers.

PubMed

van der Hart, O; Brown, P; Graafland, M

1999-02-01

This study relates trauma-induced dissociative amnesia reported in World War I (WW I) studies of war trauma to contemporary findings of dissociative amnesia in victims of childhood sexual abuse. Key diagnostic studies of post-traumatic amnesia in WW I combatants are surveyed. These cover phenomenology and the psychological dynamics of dissociation vis-à-vis repression. Descriptive evidence is cited for war trauma-induced dissociative amnesia. Posttraumatic amnesia extends beyond the experience of sexual and combat trauma and is a protean symptom, which reflects responses to the gamut of traumatic events.

ASGPR-Mediated Uptake of Multivalent Glycoconjugates for Drug Delivery in Hepatocytes.

PubMed

Monestier, Marie; Charbonnier, Peggy; Gateau, Christelle; Cuillel, Martine; Robert, Faustine; Lebrun, Colette; Mintz, Elisabeth; Renaudet, Olivier; Delangle, Pascale

2016-04-01

Liver cells are an essential target for drug delivery in many diseases. The hepatocytes express the asialoglycoprotein receptor (ASGPR), which promotes specific uptake by means of N-acetylgalactosamine (GalNAc) recognition. In this work, we designed two different chemical architectures to treat Wilson's disease by intracellular copper chelation. Two glycoconjugates functionalized with three or four GalNAc units each were shown to enter hepatic cells and chelate copper. Here, we studied two series of compounds derived from these glycoconjugates to find key parameters for the targeting of human hepatocytes. Efficient cellular uptake was demonstrated by flow cytometry using HepG2 human heptic cells that express the human oligomeric ASGPR. Dissociation constants in the nanomolar range showed efficient multivalent interactions with the receptor. Both architectures were therefore concluded to be able to compete with endogeneous asialoglycoproteins and serve as good vehicles for drug delivery in hepatocytes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DSM-5's posttraumatic stress disorder with dissociative symptoms: challenges and future directions.

PubMed

Dorahy, Martin J; van der Hart, Onno

2015-01-01

The Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition, formally recognizes a dissociative subtype of posttraumatic stress disorder (PTSD; PTSD with dissociative symptoms). This nomenclative move will boost empirical and theoretical efforts to further understand the links between dissociation, trauma, and PTSD. This article examines the empirical literature showing that patients with PTSD can be divided into 2 different groups based on their neurobiology, psychological symptom profile, history of exposure to early relational trauma, and depersonalization/derealization symptoms. It then explores the conceptual and empirical challenges of conceiving 1 of these types as reflecting a "dissociative" type of PTSD. First, this classification is based on the presence of a limited subset of dissociative symptoms (i.e., depersonalization, derealization). This sets aside an array of positive and negative psychoform and somatoform dissociative symptoms that may be related to PTSD. Second, empirical evidence suggests heightened dissociation in PTSD compared to many other disorders, indicating that dissociation is relevant to PTSD more broadly rather than simply to the so-called dissociative subtype. This article sets out important issues to be examined in the future study of dissociation in PTSD, which needs to be informed by solid conceptual understandings of dissociation.

Dissociation in Maltreated versus Nonmaltreated Preschool-Age Children.

ERIC Educational Resources Information Center

Macfie, Jenny; Cicchetti, Dante; Toth, Sheree L.

2001-01-01

A study compared the self-development of 43 typical preschool children and 155 maltreated preschool children. Each group of sexually, physically abused, and neglected preschool children showed more dissociation than did the typical children. Clinically identifiable dissociation was particularly associated with physical abuse. Severity of…

Cumulative trauma, PTSD and dissociation among Ethiopian refugees in Israel.

PubMed

Finklestein, Michal; Solomon, Zahava

2009-01-01

The aim of this study was to examine the exposure of Ethiopian refugees to pre-, peri- and post-migration stressful events and their implications for both posttraumatic stress disorder (PTSD) and dissociation. A random sample (N = 478) of three groups of refugees took part in the research ("Moses" immigrants, 1984, n = 165; "Solomon" immigrants, 1991, n = 169; "Family Reunification" immigrants, 1995, n = 144). Exposure to stressful events and posttraumatic symptoms were assessed via the Harvard Trauma Questionnaire (HTQ). Post-migration difficulties were assessed via the Post Migration Living Difficulties (PMLD) scale. Dissociation was evaluated using the Dissociation Experience Scale (DES). Significant differences were found among the groups in the rates of PTSD (27%, 15%, and 26%, respectively), but no differences were found in dissociation. A significant relationship was found between PTSD symptoms and cumulative trauma among the three groups, but no such relationship was found between dissociation and cumulative trauma. The differences among the groups were discussed in light of the unique characteristics of cumulative trauma, PTSD and dissociation among Ethiopian refugees.

Elongational flow of polymer melts at constant strain rate, constant stress and constant force

NASA Astrophysics Data System (ADS)

Wagner, Manfred H.; Rolón-Garrido, Víctor H.

2013-04-01

Characterization of polymer melts in elongational flow is typically performed at constant elongational rate or rarely at constant tensile stress conditions. One of the disadvantages of these deformation modes is that they are hampered by the onset of "necking" instabilities according to the Considère criterion. Experiments at constant tensile force have been performed even more rarely, in spite of the fact that this deformation mode is free from necking instabilities and is of considerable industrial relevance as it is the correct analogue of steady fiber spinning. It is the objective of the present contribution to present for the first time a full experimental characterization of a long-chain branched polyethylene melt in elongational flow. Experiments were performed at constant elongation rate, constant tensile stress and constant tensile force by use of a Sentmanat Extensional Rheometer (SER) in combination with an Anton Paar MCR301 rotational rheometer. The accessible experimental window and experimental limitations are discussed. The experimental data are modelled by using the Wagner I model. Predictions of the steady-start elongational viscosity in constant strain rate and creep experiments are found to be identical, albeit only by extrapolation of the experimental data to Hencky strains of the order of 6. For constant stress experiments, a minimum in the strain rate and a corresponding maximum in the elongational viscosity is found at a Hencky strain of the order of 3, which, although larger than the steady-state value, follows roughly the general trend of the steady-state elongational viscosity. The constitutive analysis also reveals that constant tensile force experiments indicate a larger strain hardening potential than seen in constant elongation rate or constant tensile stress experiments. This may be indicative of the effect of necking under constant elongation rate or constant tensile stress conditions according to the Considère criterion.

The influence of family environment on dissociation in pediatric injury patients.

PubMed

Nugent, Nicole R; Sledjeski, Eve M; Christopher, Norman C; Delahanty, Douglas L

2011-10-01

Emerging support for the roles of both early trauma and family environment in the development of dissociative symptomatology is complicated by the frequent co-occurrence of dysfunctional family environments and childhood maltreatment. The present investigation prospectively examined the influence of family environment on dissociative symptom course in 82 youths (8-18 years) who experienced accidental injury. The primary caretaker reported on six-week family environment (including family cohesion and adaptability) and on youth symptoms of dissociation prior to injury at six weeks and at six months; dissociation prior to injury was assessed via retrospective parent account at the six-week timepoint. Adolescents (aged 11-18) also reported on their own dissociative symptoms at six weeks. Latent growth modeling indicated that youth in more cohesive family environments evidenced decreased symptoms of dissociation at the six-week intercept (z = -2.80). Furthermore, parent income was negatively related to symptoms of dissociation at intercept (z = -1.96) and parent education was associated with a decrease in youth dissociation symptoms over time (z = -2.57). The present findings provide support for the importance of acute family environment in pediatric post-injury adjustment and further highlight the importance of parent resources, including income and education, in post-injury adjustment.

Nitrogen supply system based on hydrazine dissociation

NASA Technical Reports Server (NTRS)

Heppner, D. B.; Quattrone, P. D.

1981-01-01

Future long-duration manned space missions will require a method of generating N2 for cabin leakage makeup and repressurization. Life Systems, working with NASA, is developing a Nitrogen Supply Subsystem (NSS) based on the dissociation of N2H4 into a mixture of H2 and N2. The latter is separated to provide the makeup N2. Recent advances in specific hardware developments have resulted in the design and fabrication of a nominal 3.6 kg/day N2 generation module. The design integrates a N2H4 catalytic dissociator, three ammonia (NH3) dissociation stages and four H2 separation stages into a 33 kg, 14 cu dm module. A technique has been devised to alternate the NH3 dissociation and H2 separation stages to give high N2 purity in the product stream. Tests have shown the product stream to contain less than 0.5 percent H2 and 20 ppm NH3. This paper discusses the development and test activities of the NSS program. It reviews the design, configuration, operation and projected performance characteristics of a 4.4 kg/day NSS suitable for NASA's planned Space Operations Center.

Inhibition of Large-Conductance Ca2+-Activated K+ Channels by Nanomolar Concentrations of Ag+S⃞

PubMed Central

Xia, Xiaoming; Lingle, Christopher J.

2010-01-01

Silver has been widely used in various medical products because of its antibacterial properties. However, there is only limited information concerning silver-related cytotoxicity. In this study we show that Ag+ at low nanomolar concentrations (<10 nM) strongly inhibits the activity of large-conductance Ca2+-activated K+ channels (BK) (Slo1), a widely expressed and physiologically important potassium channel. The Ag+ inhibition is caused by irreversible modification on cytosolically accessible parts of the BK channel. At least four intracellular cysteines are involved in this process. In addition, at least one of these key cysteines is not accessible to the bulkier thiolate-active reagent [2-(trimethylammonium)ethyl] methanethiosulfonate bromide. One of the cysteine-less constructs generated in this study shows gating properties similar to wild-type BK channel but with much lower Ag+ sensitivity, in which the Ag+ modification rate was decreased by approximately 20-fold. The results from the present study suggest a possible contribution of BK channel inhibition to the cytotoxicity of Ag+ in humans and other species. PMID:20729303

Discovery of Nanomolar Dengue and West Nile Virus Protease Inhibitors Containing a 4-Benzyloxyphenylglycine Residue.

PubMed

Behnam, Mira A M; Graf, Dominik; Bartenschlager, Ralf; Zlotos, Darius P; Klein, Christian D

2015-12-10

The dengue virus (DENV) and West Nile Virus (WNV) NS2B-NS3 proteases are attractive targets for the development of dual-acting therapeutics against these arboviral pathogens. We present the synthesis and extensive biological evaluation of inhibitors that contain benzyl ethers of 4-hydroxyphenylglycine as non-natural peptidic building blocks synthesized via a copper-complex intermediate. A three-step optimization strategy, beginning with fragment growth of the C-terminal 4-hydroxyphenylglycine to the benzyloxy ether, followed by C- and N-terminal optimization, and finally fragment merging generated compounds with in vitro affinities in the low nanomolar range. The most promising derivative reached Ki values of 12 nM at the DENV-2 and 39 nM at the WNV proteases. Several of the newly discovered protease inhibitors yielded a significant reduction of dengue and West Nile virus titers in cell-based assays of virus replication, with an EC50 value of 3.4 μM at DENV-2 and 15.5 μM at WNV for the most active analogue.

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. Copyright 2003, Elsevier Science (USA). All rights reserved.

[Childhood traumatization, dissociation and nonsuicidal self-injurious behavior in borderline personality disorder].

PubMed

Merza, Katalin; Harmatta, János; Papp, Gábor; Kuritárné Szabó, Ildikó

2017-05-01

Childhood traumatization plays a significant role in the etiology of borderline personality disorder. Studies found a significant association between childhood traumatization, dissociation, and nonsuicidal self-injurious behavior. The aim of our study was to assess dissociation and nonsuicidal self-injury among borderline inpatients and to reveal the association between childhood traumatization, dissociation, and self-injurious behavior. The sample consisted of 80 borderline inpatients and 73 depressed control patients. Childhood traumatization, dissociation and self-injurious behavior were assessed by questionnaires. Borderline patients reported severe and multiplex childhood traumatization. Cumulative trauma score and sexual abuse were the strongest predictors of dissociation. Furthermore, we have found that cumulative trauma score and dissociation were highly predictive of self-injurious behavior. Our results suggest that self-injurious behavior and dissociation in borderline patients can be regarded as indicators of childhood traumatization. Orv Hetil. 2017; 158(19): 740-747.

Nanomolar concentrations of adrenaline induce platelet adhesion in vitro.

PubMed

Eriksson, Andreas C; Whiss, Per A

2013-01-01

Adrenaline is a platelet activator having a resting plasma concentration of <1 nmol/l that increases to a few nmol/l during stress. However, most in vitro assays only detect effects of adrenaline in micromolar concentrations. This makes it difficult to estimate the relevance of in vitro data for the in vivo situation. The aim of this study was to investigate experimental conditions in vitro that could detect platelet effects of adrenaline in nanomolar concentrations. Platelet adhesion to albumin and collagen was evaluated with a static platelet adhesion assay. Our results show that 10 nmol/l adrenaline induced platelet adhesion to albumin in platelet-rich plasma (PRP) prepared at 140 × g, while 100 nmol/l was necessary in order to increase adhesion of platelets prepared at 220 × g. The mean platelet volume was increased after preparation at 140 × g, suggesting that large reactive platelets contributed to the increased adrenaline sensitivity. At optimal Mg(2+)-concentration, adhesion to collagen was increased by 10 nmol/l adrenaline irrespective of centrifugal force applied during PRP preparation. More specifically, we defined two populations where adhesion to collagen was increased by 10 nmol/l adrenaline either upon centrifugation at 140 × g but not 220 × g or vice versa. In some experiments, platelet adhesion to collagen was induced by 3 nmol/l adrenaline, which corresponds to concentrations achieved during stress in vivo. In summary, the static adhesion assay is able to detect platelet activating effects of adrenaline very close to physiological concentrations. This is rare for in vitro assays and motivates further research about adrenergic signalling in platelets.

Dissociation and Alterations in Brain Function and Structure: Implications for Borderline Personality Disorder.

PubMed

Krause-Utz, Annegret; Frost, Rachel; Winter, Dorina; Elzinga, Bernet M

2017-01-01

Dissociation involves disruptions of usually integrated functions of consciousness, perception, memory, identity, and affect (e.g., depersonalization, derealization, numbing, amnesia, and analgesia). While the precise neurobiological underpinnings of dissociation remain elusive, neuroimaging studies in disorders, characterized by high dissociation (e.g., depersonalization/derealization disorder (DDD), dissociative identity disorder (DID), dissociative subtype of posttraumatic stress disorder (D-PTSD)), have provided valuable insight into brain alterations possibly underlying dissociation. Neuroimaging studies in borderline personality disorder (BPD), investigating links between altered brain function/structure and dissociation, are still relatively rare. In this article, we provide an overview of neurobiological models of dissociation, primarily based on research in DDD, DID, and D-PTSD. Based on this background, we review recent neuroimaging studies on associations between dissociation and altered brain function and structure in BPD. These studies are discussed in the context of earlier findings regarding methodological differences and limitations and concerning possible implications for future research and the clinical setting.

Ab initio studies of dissociative recombination

NASA Technical Reports Server (NTRS)

Guberman, Steven L.

1989-01-01

Quantum chemical calculations of the dissociative recombination of O2(+) and N2(+) are reported. An approach for calculating autoionization widths from high-principal-quantum-number Rydberg states is summarized, and an example is presented for the lowest dissociative state of O2. For O2(+), the 1Sigma(+)u state is the sole source of O(1S) from the lowest 10 vibrational levels of the ion. Rate coefficients for generating O(1S) and O(1D) at ionospheric temperatures are reported.

Cognitive behavioral hypnotherapy for dissociative disorders.

PubMed

Fine, Catherine G

2012-04-01

Dissociative disorders (DD) prevail as sequelae to overwhelming experiences in childhood. These readily formed post-traumatic responses and trance states develop in high hypnotizable subjects whose dysregulations become organized into ego states. A cognitive behavioral hypnotherapeutic treatment model will effectively contain, explore, metabolize, and resolve these life-endangering conditions. This article will detail the cognitive hypnotic world of DD patients, the relational spaces of the ego states, and the triphasic treatment mode to successfully resolve the dissociative pathology. Structured and phase appropriate hypnotic interventions will be described.

Dissociative identity disorder among adolescents: prevalence in a university psychiatric outpatient unit.

PubMed

Sar, Vedat; Onder, Canan; Kilincaslan, Ayse; Zoroglu, Süleyman S; Alyanak, Behiye

2014-01-01

The aim of this study was to determine the prevalence of dissociative identity disorder (DID) and other dissociative disorders among adolescent psychiatric outpatients. A total of 116 consecutive outpatients between 11 and 17 years of age who were admitted to the child and adolescent psychiatry clinic of a university hospital for the 1st time were evaluated using the Adolescent Dissociative Experiences Scale, adolescent version of the Child Symptom Inventory-4, Childhood Trauma Questionnaire, and McMaster Family Assessment Device. All patients were invited for an interview with the Structured Clinical Interview for DSM-IV Dissociative Disorders (SCID-D) administered by 2 senior psychiatrists in a blind fashion. There was excellent interrater reliability between the 2 clinicians on SCID-D diagnoses and scores. Among 73 participants, 33 (45.2%) had a dissociative disorder: 12 (16.4%) had DID, and 21 (28.8%) had dissociative disorder not otherwise specified. There was no difference in gender distribution, childhood trauma, or family dysfunction scores between the dissociative and nondissociative groups. Childhood emotional abuse and family dysfunction correlated with self-reported dissociation. Of the dissociative adolescents, 93.9% had an additional psychiatric disorder. Among them, only separation anxiety disorder was significantly more prevalent than in controls. Although originally designed for adults, the SCID-D is promising for diagnosing dissociative disorders in adolescents, its modest congruence with self-rated dissociation and lack of relationship between diagnosis and childhood trauma and family dysfunction suggest that the prevalence rates obtained with this instrument originally designed for adults must be replicated. The introduction of diagnostic criteria for adolescent DID in revised versions of the Diagnostic and Statistical Manual of Mental Disorders, Fifth Edition, would refine the assessment of dissociative disorders in this age group.

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,…

Dissociation, childhood trauma, and ataque de nervios among Puerto Rican psychiatric outpatients.

PubMed

Lewis-Fernández, Roberto; Garrido-Castillo, Pedro; Bennasar, Mari Carmen; Parrilla, Elsie M; Laria, Amaro J; Ma, Guoguang; Petkova, Eva

2002-09-01

This study examined the relationships of dissociation and childhood trauma with ataque de nervios. Forty Puerto Rican psychiatric outpatients were evaluated for frequency of ataque de nervios, dissociative symptoms, exposure to trauma, and mood and anxiety psychopathology. Blind conditions were maintained across assessments. Data for 29 female patients were analyzed. Among these 29 patients, clinician-rated dissociative symptoms increased with frequency of ataque de nervios. Dissociative Experiences Scale scores and diagnoses of panic disorder and dissociative disorders were also associated with ataque frequency, before corrections were made for multiple comparisons. The rate of childhood trauma was uniformly high among the patients and showed no relationship to dissociative symptoms and disorder or number of ataques. Frequent ataques de nervios may, in part, be a marker for psychiatric disorders characterized by dissociative symptoms. Childhood trauma per se did not account for ataque status in this group of female outpatients.

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... system. (a) Identification. A spectacle dissociation test system is an AC-powered or battery-powered device, such as a Lancaster test system, that consists of a light source and various filters, usually red...

21 CFR 886.1910 - Spectacle dissociation test system.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Spectacle dissociation test system. 886.1910... system. (a) Identification. A spectacle dissociation test system is an AC-powered or battery-powered device, such as a Lancaster test system, that consists of a light source and various filters, usually red...

21 CFR 886.1910 - Spectacle dissociation test system.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Spectacle dissociation test system. 886.1910... system. (a) Identification. A spectacle dissociation test system is an AC-powered or battery-powered device, such as a Lancaster test system, that consists of a light source and various filters, usually red...

21 CFR 886.1910 - Spectacle dissociation test system.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Spectacle dissociation test system. 886.1910... system. (a) Identification. A spectacle dissociation test system is an AC-powered or battery-powered device, such as a Lancaster test system, that consists of a light source and various filters, usually red...

21 CFR 886.1910 - Spectacle dissociation test system.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Spectacle dissociation test system. 886.1910... system. (a) Identification. A spectacle dissociation test system is an AC-powered or battery-powered device, such as a Lancaster test system, that consists of a light source and various filters, usually red...

Separating Item and Order Information through Process Dissociation

ERIC Educational Resources Information Center

Nairne, James S.; Kelley, Matthew R.

2004-01-01

In the present paper, we develop and apply a technique, based on the logic of process dissociation, for obtaining numerical estimates of item and order information. Certain variables, such as phonological similarity, are widely believed to produce dissociative effects on item and order retention. However, such beliefs rest on the questionable…

Trait dissociation and commission errors in memory reports of emotional events.

PubMed

Merckelbach, Harald; Zeles, Gwen; Van Bergen, Saskia; Giesbrecht, Timo

2007-01-01

In 2 studies we examined whether trait dissociation is related to spontaneous commission errors (reports of events that did not occur) in free recall of emotional events. We also explored whether the functional locus of the dissociation-commission link is related to repeated retrieval or shallow encoding. In Experiment 1 participants were exposed to a staged incident and were repeatedly asked to add more information to their written accounts of the event. Dissociation levels were related to commission errors, indicating that people who report many dissociative experiences tend to make more commission errors. However, it was not the case that the overall increase in commission errors over successive retrieval attempts was typical for high dissociative participants. In Experiment 2 participants saw a video fragment of a severe car accident. During the video, half the participants performed a dual task, and the other half did not. Participants performing the dual task made more commission errors than controls, but this effect was not more pronounced in those with high trait dissociation scores. These studies show that there is a link between dissociation and spontaneous commission errors in memory reports of emotional events, but the functional locus of this link remains unclear.

Dissociative Amnesia and DSM-IV-TR Cluster C Personality Traits.

PubMed

Leong, Stephanie; Waits, Wendi; Diebold, Carroll

2006-01-01

Dissociative amnesia is a disorder characterized by retrospectively reported memory gaps. These gaps involve an inability to recall personal information, usually of a traumatic or stressful nature. Dissociative amnesia most commonly occurs in the presence of other psychiatric conditions, particularly personality disorders. In the literature and in clinical practice, it is often associated with DSM-IV-TR Cluster B personality disorders. However, there is evidence to suggest that dissociative amnesia may be more likely to occur among individuals with Cluster C personality disorders. Presented here is a discussion of the types of memory loss, two cases of dissociative amnesia occurring in patients with Cluster C psychopathology, and a focused literature review.

Mechanistic Insight into Caffeine-Oxalic Cocrystal Dissociation in Formulations: Role of Excipients.

PubMed

Duggirala, Naga Kiran; Vyas, Amber; Krzyzaniak, Joseph F; Arora, Kapildev K; Suryanarayanan, Raj

2017-11-06

Caffeine-oxalic acid cocrystal, widely reported to be stable under high humidity, dissociated in the presence of numerous pharmaceutical excipients. In cocrystal-excipient binary systems, the water mediated dissociation reaction occurred under pharmaceutically relevant storage conditions. Powder X-ray diffractometry was used to identify the dissociated products obtained as a consequence of coformer-excipient interaction. The proposed cocrystal dissociation mechanism involved water sorption, dissolution of cocrystal and excipient in the sorbed water, proton transfer from oxalic acid to the excipient, and formation of metal salts and caffeine hydrate. In compressed tablets with magnesium stearate, the cocrystal dissociation was readily discerned from the appearance of peaks attributable to caffeine hydrate and stearic acid. Neutral excipients provide an avenue to circumvent the risk of water mediated cocrystal dissociation.

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.

Dissociative part-dependent resting-state activity in dissociative identity disorder: a controlled FMRI perfusion study.

PubMed

Schlumpf, Yolanda R; Reinders, Antje A T S; Nijenhuis, Ellert R S; Luechinger, Roger; van Osch, Matthias J P; Jäncke, Lutz

2014-01-01

In accordance with the Theory of Structural Dissociation of the Personality (TSDP), studies of dissociative identity disorder (DID) have documented that two prototypical dissociative subsystems of the personality, the "Emotional Part" (EP) and the "Apparently Normal Part" (ANP), have different biopsychosocial reactions to supraliminal and subliminal trauma-related cues and that these reactions cannot be mimicked by fantasy prone healthy controls nor by actors. Arterial spin labeling perfusion MRI was used to test the hypotheses that ANP and EP in DID have different perfusion patterns in response to rest instructions, and that perfusion is different in actors who were instructed to simulate ANP and EP. In a follow-up study, regional cerebral blood flow of DID patients was compared with the activation pattern of healthy non-simulating controls. Compared to EP, ANP showed elevated perfusion in bilateral thalamus. Compared to ANP, EP had increased perfusion in the dorsomedial prefrontal cortex, primary somatosensory cortex, and motor-related areas. Perfusion patterns for simulated ANP and EP were different. Fitting their reported role-play strategies, the actors activated brain structures involved in visual mental imagery and empathizing feelings. The follow-up study demonstrated elevated perfusion in the left temporal lobe in DID patients, whereas non-simulating healthy controls had increased activity in areas which mediate the mental construction of past and future episodic events. DID involves dissociative part-dependent resting-state differences. Compared to ANP, EP activated brain structures involved in self-referencing and sensorimotor actions more. Actors had different perfusion patterns compared to genuine ANP and EP. Comparisons of neural activity for individuals with DID and non-DID simulating controls suggest that the resting-state features of ANP and EP in DID are not due to imagination. The findings are consistent with TSDP and inconsistent with the idea

Dissociative subtype of DSM-5 posttraumatic stress disorder in U.S. veterans.

PubMed

Tsai, Jack; Armour, Cherie; Southwick, Steven M; Pietrzak, Robert H

2015-01-01

The Diagnostic and Statistical Manual of Mental Disorders, 5th edition (DSM-5) formally introduced a dissociative subtype of posttraumatic stress disorder (PTSD). This study examined the proportion of U.S. veterans with DSM-5 PTSD that report dissociative symptoms; and compared veterans with PTSD with and without the dissociative subtype and trauma-exposed controls on sociodemographics, clinical characteristics, and quality of life. Multivariable analyses were conducted on a nationally representative sample of 1484 veterans from the National Health and Resilience in Veterans Study (second baseline survey conducted September-October, 2013). Of the 12.0% and 5.2% of veterans who screened positive for lifetime and past-month DSM-5 PTSD, 19.2% and 16.1% screened positive for the dissociative subtype, respectively. Among veterans with PTSD, those with the dissociative subtype reported more severe PTSD symptoms, comorbid depressive and anxiety symptoms, alcohol use problems, and hostility than those without the dissociative subtype. Adjusting for PTSD symptom severity, those with the dissociative subtype continued to report more depression and alcohol use problems. These results underscore the importance of assessing, monitoring, and treating the considerable proportion of veterans with PTSD and dissociative symptoms. Published by Elsevier Ltd.

[Low dose naltrexone in the treatment of dissociative symptoms].

PubMed

Pape, W; Wöller, W

2015-03-01

Following the hypothesis that blocking opioid receptors leads to a decline in opiate-modulated dissociative phenomena, experiences with naltrexone as medication for dissociative symptoms have been gained since 1999 (mainly in doses of 25-100 mg/day). In this study patients with severe trauma-related and dissociative disorders were treated with naltrexone in doses of 2-6 mg/day (0.06 mg/kg body weight). The low dose treatment with naltrexone proved to be effective whereby 11 out of 15 patients reported immediate positive effects and 7 described a lasting helpful effect. The majority of patients who felt positive effects reported a clearer perception of both their surroundings and their inner life. Assessment of reality and dealing with it improved as did the perception of their own body and affects as well as self-regulation. The treatment was very low in side effects. Treatment with low-dose naltrexone may be a helpful element in the treatment of patients with complex posttraumatic stress disorder. However, it has to be realized that the decrease of dissociation may lead patients to a not yet resolvable challenge, in as much as dissociation had previously been a necessary mechanism of self-protection.

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…

Multiple Personality and the Pathological Dissociation of Self.

ERIC Educational Resources Information Center

Price, Reese E.

This paper considers the condition of Multiple Personality Disorder (MPD), which is defined as a separation of alternating personalities by rigid boundaries and amnestic barriers. It is proposed that MPD represents the end of a continuum of a defensive dissociation of the self that can result when a child employs a dissociative splitting of self…

Dissociative symptoms and mother's marital status in young adult population.

PubMed

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

2015-01-01

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.

General features of the dissociative recombination of polyatomic molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, S. T.; Jungen, Ch.; Schneider, I. F.

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.

General features of the dissociative recombination of polyatomic molecules

DOE PAGES

Pratt, S. T.; Jungen, Ch.; Schneider, I. F.; ...

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.

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.

Trauma, Dissociation, and Antiretroviral Adherence among Persons Living with HIV/AIDS

PubMed Central

Keuroghlian, Alex S.; Kamen, Charles S.; Neri, Eric; Lee, Susanne; Liu, Rhianon; Gore-Felton, Cheryl

2011-01-01

Background There are approximately 1,000,000 persons living with HIV/AIDS (PLH) in the United States; to reduce rates of new infection and curb disease progression, adherence to HIV medication among PLH is critical. Despite elevated trauma rates in PLH, no studies to date have investigated the relationship between dissociation, a specific symptom of trauma, and HIV medication adherence. We hypothesized that Post-Traumatic Stress Disorder (PTSD) symptoms would be associated with lower adherence, and that dissociation would moderate this relationship. Methods Forty-three individuals with HIV were recruited from community-based clinics to participate in a cross-sectional study. The relationship of trauma, dissociation, and their interaction to the probability of antiretroviral adherence was assessed using a hierarchical binary logistic regression analysis. Results Among 38 eligible participants, greater PTSD was associated with lower odds of adherence (OR = .92, p < .05). Dissociation moderated the effect of PTSD on adherence, resulting in lower odds of adherence (OR = .95, p < .05). PTSD symptoms were significantly associated with lower odds of adherence in individuals reporting high levels of dissociation (OR = .86, p < .05) but not in those reporting low levels of dissociation (OR = 1.02, p > .05). Conclusions This is the first study to demonstrate a relationship between dissociation and medication adherence. Findings are discussed in the context of clinical management of PLH with trauma histories and the need for interventions targeting dissociative symptomatology to optimize adherence. PMID:21636097

Perseveration induces dissociative uncertainty in obsessive-compulsive disorder.

PubMed

Giele, Catharina L; van den Hout, Marcel A; Engelhard, Iris M; Dek, Eliane C P; Toffolo, Marieke B J; Cath, Danielle C

2016-09-01

Obsessive compulsive (OC)-like perseveration paradoxically increases feelings of uncertainty. We studied whether the underlying mechanism between perseveration and uncertainty is a reduced accessibility of meaning ('semantic satiation'). OCD patients (n = 24) and matched non-clinical controls (n = 24) repeated words 2 (non-perseveration) or 20 times (perseveration). They decided whether this word was related to another target word. Speed of relatedness judgments and feelings of dissociative uncertainty were measured. The effects of real-life perseveration on dissociative uncertainty were tested in a smaller subsample of the OCD group (n = 9). Speed of relatedness judgments was not affected by perseveration. However, both groups reported more dissociative uncertainty after perseveration compared to non-perseveration, which was higher in OCD patients. Patients reported more dissociative uncertainty after 'clinical' perseveration compared to non-perseveration.. Both parts of this study are limited by some methodological issues and a small sample size. Although the mechanism behind 'perseveration → uncertainty' is still unclear, results suggest that the effects of perseveration are counterproductive. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Process dissociation and mixture signal detection theory.

PubMed

DeCarlo, Lawrence T

2008-11-01

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 analyzed study. The results suggest that a process other than recollection may be involved in the process dissociation procedure.

Stroop performance, dissociation, and trauma exposure in a community sample of children.

PubMed

DePrince, Anne P; Weinzierl, Kristin M; Combs, Melody D

2008-01-01

Extending previous research with adults, the current study examined Stroop task performance under selective and divided attention demands in a community sample of school-age children (N = 97). Stroop interference scores in both attention conditions were calculated. Higher levels of child-reported dissociation were associated with better interference control under divided attention conditions and worse control under selective attention conditions; lower levels of dissociation were associated with the opposite pattern. Both family violence exposure and Stroop interaction scores explained unique variance in dissociation scores. Although research with adults has generally assumed or implied that cognitive correlates of dissociation are a consequence of dissociation, the current findings with school-age children suggest that future research should evaluate executive function performance (in this case, interference control) as a possible risk factor for dissociation.

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.

Peroxide Bond Driven Dissociation of Hydroperoxy-Cholesterol Esters Following Collision Induced Dissociation

NASA Astrophysics Data System (ADS)

Hutchins, Patrick M.; Murphy, Robert C.

2011-05-01

Oxidative modification of polyunsaturated fatty acids, which occurs through enzymatic and nonenzymatic processes, is typically initiated by the attachment of molecular oxygen to an unsaturated fatty acyl chain forming a lipid hydroperoxide (LOOH). Enzymatic pathways are critical for cellular homeostasis but aberrant lipid peroxidation has been implicated in important pathologies. Analysis of primary oxidation products such as hydroperoxides has proven to be challenging for a variety of reasons. While negative ion electrospray ionization has been used for the specific detection of some LOOH species, hydroperoxide dehydration in the ion source has been a significant drawback. Here we describe positive ion electrospray ionization of ammoniated 13-hydroperoxy-9Z, 11E-octadecadienoyl cholesterol and 9-hydroperoxy-10E, 12Z-octadecadienoyl cholesterol, [M + NH4]+, following normal phase high-pressure liquid-chromatography. Dehydration in the ion source was not prevalent and the ammoniated molecular ion was the major species observed. Collisionally induced dissociation of the two positional isomers yielded unique product ion spectra resulting from carbon-carbon cleavages along their acyl chains. Further investigation of this behavior revealed that complex collision induced dissociations were initiated by scission of the hydroperoxide bond that drove subsequent acyl chain cleavages. Interestingly, some of the product ions retained the ammonium nitrogen through the formation of covalent carbon-nitrogen or oxygen-nitrogen bonds. These studies were carried out using hydroperoxy-octadecadienoate cholesteryl esters as model compounds, however the observed mechanisms of [LOOH + NH4]+ ionization and dissociation are likely applicable to the analysis of other lipid hydroperoxides and may serve as the basis for selective LOOH detection as well as aid in the identification of unknown lipid hydroperoxides.

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.

Dissociative Amnesia and DSM-IV-TR Cluster C Personality Traits

PubMed Central

Waits, Wendi; Diebold, Carroll

2006-01-01

Dissociative amnesia is a disorder characterized by retrospectively reported memory gaps. These gaps involve an inability to recall personal information, usually of a traumatic or stressful nature. Dissociative amnesia most commonly occurs in the presence of other psychiatric conditions, particularly personality disorders. In the literature and in clinical practice, it is often associated with DSM-IV-TR Cluster B personality disorders. However, there is evidence to suggest that dissociative amnesia may be more likely to occur among individuals with Cluster C personality disorders. Presented here is a discussion of the types of memory loss, two cases of dissociative amnesia occurring in patients with Cluster C psychopathology, and a focused literature review. PMID:21103150

Dissociative and double photoionization of CO from threshold to 90 A

NASA Technical Reports Server (NTRS)

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

1981-01-01

Partial cross sections for molecular photoionization (CO(+)), dissociative photoionization (C(+) and O(+)), and dissociative double photoionization (C(2+)) in CO have been measured from their thresholds to 90 A using techniques of mass spectrometry. The results are compared with data reported previously. Several peaks observed in the cross section curves for dissociated fragments are tentatively assigned by comparing with those in the photoelectron spectra reported for CO. It is concluded that the shoulder in the total absorption cross section curve between 400 and 90 A results solely from the dissociative ionization processes.

Cell-penetrating cationic siRNA and lipophilic derivatives efficient at nanomolar concentrations in the presence of serum and albumin.

PubMed

Perche, Phanélie; Nothisen, Marc; Bagilet, Jérémy; Behr, Jean-Paul; Kotera, Mitsuharu; Remy, Jean-Serge

2013-08-28

Despite its considerable interest in human therapy, in vivo siRNA delivery is still suffering from hurdles of vectorization. We have shown recently efficient gene silencing by non-vectorized cationic siRNA. Here, we describe the synthesis and in vitro evaluation of new amphiphilic cationic siRNA. C₁₂-, (C₁₂)₂- and cholesteryl-spermine(x)-siRNA were capable of luciferase knockdown at nanomolar concentrations without vectorization (i.e. one to two orders of magnitude more potent than commercially available cholesteryl siRNA). Moreover, incubation in the presence of serum did not impair their efficiency. Finally, amphiphilic cationic siRNA was pre-loaded on albumin. In A549Luc cells in the presence of serum, these siRNA conjugates were highly effective and had low toxicity. Copyright © 2013. Published by Elsevier B.V.

Dissociative disorder manifesting for underlying adolescent hemi-parkinsonism: New chronology for old mummies.

PubMed

Jha, Shailesh; Garg, Amit; Khanna, Amit

2015-08-01

Dissociative symptoms can be induced by a variety of conditions that can either coexist or mimic each other in clinical presentation. In coexisting dissociative disorder with medical illness, the causality remains uncertain, but sometime its role as nidus for dissociative symptoms just cannot be ruled out. The origin of "organic dissociative disorder" is undoubtedly found by various authors who demonstrated that a high percentage of patients with dissociative symptoms present with some form of neurological insult before developing the symptom. Herein we report on a case of adolescent onset hemi-parkinsonism with coexisting dissociative disorder. Copyright © 2015 Elsevier B.V. All rights reserved.

Treatment of trauma- and abuse-related dissociative symptom disorders in children and adolescents.

PubMed

Weber, Scott

2009-02-01

Dissociation is believed to be one of the most common underlying psychological processes among children and adolescents receiving mental health treatment, but most of the dissemination of information about dissociation has occurred among psychiatrists and psychologists. Modes of treatment for dissociation as it affects children and adolescents are described. Current research and practice scholarly articles on treatment of children and adolescents for dissociation and dissociative symptom disorders were accessed and critically reviewed. Prognosis in children and adolescents can vary widely among patients and between the specific types of dissociation disorder; however, expert clinicians and researchers agree that early, intense treatment offers the greatest possibility of full recovery.

Axis-I comorbidity in female patients with dissociative identity disorder and dissociative identity disorder not otherwise specified.

PubMed

Rodewald, Frauke; Wilhelm-Göling, Claudia; Emrich, Hinderk M; Reddemann, Luise; Gast, Ursula

2011-02-01

The aim of this study was to investigate axis-I comorbidity in patients with dissociative identity disorder (DID) and dissociative disorder not otherwise specified (DDNOS). Using the Diagnostic Interview for Psychiatric Disorders, results from patients with DID (n = 44) and DDNOS (n = 22) were compared with those of patients with posttraumatic stress disorder (PTSD) (n = 13), other anxiety disorders (n = 14), depression (n = 17), and nonclinical controls (n = 30). No comorbid disorders were found in nonclinical controls. The average number of comorbid disorders in patients with depression or anxiety was 0 to 2. Patients with dissociative disorders averagely suffered from 5 comorbid disorders. The most prevalent comorbidity in DDNOS and DID was PTSD. Comorbidity profiles of patients with DID and DDNOS were very similar to those in PTSD (high prevalence of anxiety, somatoform disorders, and depression), but differed significantly from those of patients with depression and anxiety disorders. These findings confirm the hypothesis that PTSD, DID, and DDNOS are phenomenologically related syndromes that should be summarized within a new diagnostic category.

Dissociative seizures: a challenge for neurologists and psychotherapists.

PubMed

Fritzsche, Kurt; Baumann, Kathrin; Götz-Trabert, Katrin; Schulze-Bonhage, Andreas

2013-04-01

The prevalence of dissociative seizures is between 2 and 33 sufferers per 100,000 persons. 70% of sufferers are women. Dissociative seizures markedly impair quality of life. Their close superficial resemblance to epileptic seizures makes them hard to diagnose. Selective literature search in PubMed and PsycINFO. Persons with dissociative seizures constitute a mixed group with a wide variety of predisposing, precipitating, and maintaining factors. Some 90% have comorbid psychiatric disorders such as depression, anxiety, somatoform disorders, personality disorders, or post-traumatic stress disorder. Video-EEG monitoring enables highly reliable diagnosis. Psychotherapy is considered the treatment of first choice; in prospective studies, it has been found to lower the frequency of dissociative seizures by at least 50%, or to eliminate them completely, in 50% to 80% of patients. An individually tailored combination of behavioral therapeutic, imagery-based, and psychodynamic approaches seems reasonable. For the treatment of psychiatric comorbidities, psychotherapy is indicated, in combination with psychoactive drugs if necessary. Before any treatment is provided, the diagnosis should be communicated to the patient in an appropriate way, ideally by both the neurologist and the psychotherapist, so that the patient can develop an alternative disease model. When the diagnosis of dissociative seizures has been made, psychotherapy is indicated, possibly in combination with psychoactive medication, in the setting of long-term treatment provided in collaboration by the neurologist, psychiatrist, psychotherapist, and family physician. Further randomized trials are needed to determine which treatments are best for which subgroups of patients.

Negative words enhance recognition in nonclinical high dissociators: An fMRI study.

PubMed

de Ruiter, Michiel B; Veltman, Dick J; Phaf, R Hans; van Dyck, Richard

2007-08-01

Memory encoding and retrieval were studied in a nonclinical sample of participants that differed in the amount of reported dissociative experiences (trait dissociation). Behavioral as well as functional imaging (fMRI) indices were used as convergent measures of memory functioning. In a deep vs. shallow encoding paradigm, the influence of dissociative style on elaborative and avoidant encoding was studied, respectively. Furthermore, affectively neutral and negative words were presented, to test whether the effects of dissociative tendencies on memory functioning depended on the affective valence of the stimulus material. Results showed that (a) deep encoding of negative vs. neutral stimuli was associated with higher levels of semantic elaboration in high than in low dissociators, as indicated by increased levels of activity in hippocampus and prefrontal cortex during encoding and higher memory performance during recognition, (b) high dissociators were generally characterized by higher levels of conscious recollection as indicated by increased activity of the hippocampus and posterior parietal areas during recognition, (c) nonclinical high dissociators were not characterized by an avoidant encoding style. These results support the notion that trait dissociation in healthy individuals is associated with high levels of elaborative encoding, resulting in high levels of conscious recollection. These abilities, in addition, seem to depend on the salience of the presented stimulus material.

Enhanced accessibility of ignored neutral and negative items in nonclinical dissociative individuals.

PubMed

Chiu, Chui-De

2018-01-01

While clinical studies showed paradoxical memory phenomena, including the intrusion and amnesia of stressful experiences that are features of dissociation, the results of laboratory studies on dissociative individuals' forgetting of experimental stimuli through cognitive control varied. Some studies demonstrated ineffective inhibition, and others found that dissociative individuals could remember fewer trauma words in a divided-attention context. Dissociative individuals may utilize superior cognitive disengagement to forget the representations. This hypothesis was tested in nonclinical individuals with high, medium, and low dissociation proneness. In the study phase, the participants learned several lists of experimental words and kept updating working memory by remembering the last four items on a list (target) and ignoring those non-target items. A recognition test was then conducted. The high dissociation group performed better on updating working memory. However, the accessibility of the representations of neutral and negative non-target items was elevated. Dissociative individuals disengaged attention effectively from items they intended to ignore, and the representations of the ignored items were more accessible when cues were available. Copyright © 2017 Elsevier Inc. All rights reserved.

Role of dissociation in "false drug allergy".

PubMed

Rodriguez-Cano, Teresa; Beato-Fernandez, Luis; Galindo-Bonilla, Pedro

2006-01-01

The aim of the present study was to analyze the influence of dissociation on the "false allergy" phenomenon. Fifty-five individuals (11 males and 44 females) who consecutively presented for the study of their suspected drug allergy were assessed. After the challenge test, false allergy was found in 39.3% and placebo positive response in 12.5% of the patients. Seven patients (12.5%) scored above the cut-off point of 20 on the Dissociative Experiences Scale (DES), and 5 out of this group (71.4%) fit in the "false allergy" group. Pathological scores on the DES were associated with the diagnosis of "false allergy" (OR = 9.583, 95% CI = 1.002, 91.621). The effect of age, gender, and other psychopathological variables was controlled. High levels of dissociation might predispose to false drug allergy, which could complicate pharmacological treatment and therefore increase the patient's complaints and demands for medical attention.

Dissociation and symptoms of culture-bound syndromes in North America: a preliminary study.

PubMed

Ross, Colin A; Schroeder, Elizabeth; Ness, Laura

2013-01-01

The aim of this study was to determine whether classical culture-bound syndromes occur among psychiatric inpatients with dissociative disorders in North America. The Dissociative Trance Disorder Interview Schedule, the Dissociative Experiences Scale, and the Dissociative Disorders Interview Schedule were administered to 100 predominantly Caucasian, American, English-speaking trauma program inpatients at a hospital in the United States. The participants reported high rates of childhood physical and/or sexual abuse (87%), dissociative disorders (73%), and membership in the dissociative taxon (78%). They also reported a wide range of possession experiences and exorcism rituals, as well as the classical culture-bound syndromes of latah, bebainan, amok, and pibloktoq. Our data are consistent with the view that possession and classical culture-bound syndromes are predominantly dissociative in nature and not really culture-bound from the perspective of Caucasian, English-speaking America.

Brain functional integration: an epidemiologic study on stress-producing dissociative phenomena.

PubMed

Sperandeo, Raffaele; Monda, Vincenzo; Messina, Giovanni; Carotenuto, Marco; Maldonato, Nelson Mauro; Moretto, Enrico; Leone, Elena; De Luca, Vincenzo; Monda, Marcellino; Messina, Antonietta

2018-01-01

Dissociative phenomena are common among psychiatric patients; the presence of these symptoms can worsen the prognosis, increasing the severity of their clinical conditions and exposing them to increased risk of suicidal behavior. Personality disorders as long duration stressful experiences may support the development of dissociative phenomena. In 933 psychiatric outpatients consecutively recruited, presence of dissociative phenomena was identified with the Dissociative Experience Scale (DES). Dissociative phenomena were significantly more severe in the group of people with mental disorders and/or personality disorders. All psychopathologic traits detected with the symptom checklist-90-revised had a significant correlation with the total score on the DES. Using total DES score as the dependent variable, a linear regression model was constructed. Mental and personality disorders which were associated with greater severity of dissociative phenomena on analysis of variance were included as predictors; scores from the nine scales of symptom checklist-90-revised, significantly correlated to total DES score, were used as covariates. The model consisted of seven explanatory variables (four factors and three covariates) explaining 82% of variance. The four significant factors were the presence of borderline and narcissistic personality disorder, substance abuse disorders and psychotic disorders. Significant covariates were psychopathologic traits of anger, psychoticism and obsessiveness. This study, confirming Janet's theory, explains that, mental disorders and psychopathologic experiences of patients can configure the chronic stress condition that produces functional damage to the adaptive executive system. The symptoms of dissociative depersonalization/derealization and dissociative amnesia can be explained, in large part, through their current and previous psychopathologic experiences.

Brain functional integration: an epidemiologic study on stress-producing dissociative phenomena

PubMed Central

Messina, Giovanni; Carotenuto, Marco; Maldonato, Nelson Mauro; Moretto, Enrico; Leone, Elena; De Luca, Vincenzo; Monda, Marcellino; Messina, Antonietta

2018-01-01

Dissociative phenomena are common among psychiatric patients; the presence of these symptoms can worsen the prognosis, increasing the severity of their clinical conditions and exposing them to increased risk of suicidal behavior. Personality disorders as long duration stressful experiences may support the development of dissociative phenomena. In 933 psychiatric outpatients consecutively recruited, presence of dissociative phenomena was identified with the Dissociative Experience Scale (DES). Dissociative phenomena were significantly more severe in the group of people with mental disorders and/or personality disorders. All psychopathologic traits detected with the symptom checklist-90-revised had a significant correlation with the total score on the DES. Using total DES score as the dependent variable, a linear regression model was constructed. Mental and personality disorders which were associated with greater severity of dissociative phenomena on analysis of variance were included as predictors; scores from the nine scales of symptom checklist-90-revised, significantly correlated to total DES score, were used as covariates. The model consisted of seven explanatory variables (four factors and three covariates) explaining 82% of variance. The four significant factors were the presence of borderline and narcissistic personality disorder, substance abuse disorders and psychotic disorders. Significant covariates were psychopathologic traits of anger, psychoticism and obsessiveness. This study, confirming Janet’s theory, explains that, mental disorders and psychopathologic experiences of patients can configure the chronic stress condition that produces functional damage to the adaptive executive system. The symptoms of dissociative depersonalization/derealization and dissociative amnesia can be explained, in large part, through their current and previous psychopathologic experiences. PMID:29296086

Temperament and character traits in patients with conversion disorder and their relations with dissociation.

PubMed

Sarisoy, Gökhan; Kaçar, Ö Mer Faruk; Öztürk, Arif; Yilman, Tuba; Mor, Sema; Özturan, Deniz Deniz; Yazici, Neslihan; Gümüş, Kübra

2015-12-01

The purpose of this study was to investigate temperament and character traits in patients with conversion disorder and the relation of these traits with dissociative symptoms. Sixty patients (60) diagnosed with conversion disorder according to DSM-IV-TR and 60 healthy volunteers were included in the study. All participants' temperament and character traits were determined using Cloninger's Temperament and Character Inventory (TCI). Patients with conversion disorder were divided into two subgroups using the Dissociative Experiences Scale (DES), dissociative (n=30, 50%) and non-dissociative (n=30, 50%). The two conversion disorder subgroups were compared with the control group in terms of temperament and character traits. Correlation analysis was also performed between TCI and DES scores in the entire conversion group. Novelty seeking (NS) scores were lower in both the dissociative and non-dissociative groups compared to the control group. Harm avoidance (HA) scores were higher in the dissociative group than in the control group. Reward dependence (RD) scores were lower in the dissociative group than in the non-dissociative and control group. Self-directedness (SD) scores were lower in the dissociative group than in the control group. Self-transcendence (ST) scores were higher in the dissociative group than in the non-dissociative group. DES scores were negatively correlated with RD and SD scores in the entire conversion group and positively correlated with ST scores. Low NS temperament traits may be associated with conversion disorder. High HA and low RD temperament traits and low SD and high ST character traits may be associated with pathological dissociation in patients with conversion disorder.

Early Indicators of Pathological Dissociation in Sexually Abused Children.

ERIC Educational Resources Information Center

McElroy, Linda Provus

1992-01-01

This paper reviews factors in the professional neglect of multiple personality disorder (MPD) and sexual abuse in childhood, as well as recent diagnostic developments in childhood dissociative disorders. The identification of subtle dissociative symptomatology in children is illustrated, and two case examples are presented. (Author)

Identifying dissociative identity disorder: a self-report and projective study.

PubMed

Scroppo, J C; Drob, S L; Weinberger, J L; Eagle, P

1998-05-01

This study compared 21 female adult psychiatric patients diagnosed with dissociative identity disorder (DID) with 21 female adult nondissociative psychiatric patients to determine whether DID patients exhibit a distinguishing set of clinical features, and perceptual, attentional, and cognitive processes. Participants were assessed with the Dissociative Disorders Interview Schedule to assess diagnostic status. Group scores on the Dissociative Experiences Scale, Tellegen Absorption Scale, Childhood Trauma Questionnaire, Brief Symptom Inventory, and the Rorschach test were compared. DID participants reported earlier and more severe childhood trauma, more dissociative symptoms, and a greater propensity for altered states of consciousness. The DID participants also exhibited increased projective and imaginative activity, a diminished ability to integrate mental contents, a complex and driven cognitive style, and a highly unconventional view of reality.

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.

The possessions at Loudun: tracking the discourse of dissociation.

PubMed

Stephenson, Craig E

2017-09-01

Embedded in the history of dissociation is the best known case of possession in European history, the 17 th century possessions at Loudun, France (1632-1638). The exorcisms and the trial drew crowds from all over Europe, the outcome prefiguring the direction in which the Western science of mind would be carried. The published debate about the possessed and obsessed Ursuline nuns of Loudun spans four centuries. One can track how theorizing about dissociation changed over time, with psychological contributions by Jean Martin Charcot, Georges Gilles de la Tourette, Pierre Janet, Michel Foucault and Michel de Certeau. Freud's psychoanalytic notion of demonological neurosis emphasized defensive strategies and a diabolic parody of adulthood. Jung's concepts of demonism and possession highlighted dissociated complexes that assimilate the ego and unseat the self, rendering a life 'provisional'. Dissociation as possession provides a through-line in Jung's Collected Works, from his 1902 dissertation to one of the last essays he wrote, in 1961. Within the context of psychotherapy, therapists and patients work towards psychological containment, consciously reorienting themselves to the presence of unconscious factors, personifying, embodying and thereby incorporating images of dissociated Otherness into the experience of selfhood. © 2017, The Society of Analytical Psychology.

First-principles study of molecular NO dissociation on Ir(100) surface

NASA Astrophysics Data System (ADS)

Erikat, I. A.; Hamad, B. A.; Khalifeh, J. M.

2014-02-01

The dissociation of NO on Ir(100) surface is investigated using density functional theory (DFT). The pathway and transition state (TS) of the dissociation of NO molecule are determined using climbing image nudge elastic band (CI-NEB). The prerequisite state of NO dissociation is determining the most stable sites of the reactant and products. We found that the most energetically stable sites are the hollow for N atom and the bridge for NO molecule as well as O atom. We found that the bending of NO is the first step of the dissociation reaction due to the increase of the back-donation from the d-band of Ir to 2 π ∗ orbital of NO, which causes the weakening of NO bond. The dissociation energy barrier of NO molecule on Ir(100) surface is 0.49 eV.

Somatoform and dissociative disorders in children and adolescents: A comparative study

PubMed Central

Malhotra, Savita; Singh, Gagandeep; Mohan, Ashwin

2005-01-01

Background: Somatoform and dissociative (conversion) disorders in adults have been reported to have a close relationship because of a diagnostic overlap and comparable aetiological models. The literature on these disorders in children and adolescents is scarce. Aim: The present study attempted to compare these two disorders in children and adolescents since antecedents of these disorders are said to be laid in childhood. Methods: Case files of 118 patients (69 of somatoform disorders and 49 of dissociative disorders) were reviewed and the two groups were compared with respect to sociodemographic profile, clinical profile, neurotic traits, behavioural problems, temperament, intelligence and family dysfunction. Results: Age at presentation and intelligence were significantly higher in those with somatoform disorders than in those with dissociative disorders. Patients with dissociative disorders had a significantly higher number of co-morbid somatoform symptoms. Conclusion: Somatoform and dissociative disorders are closely linked.

Fractionating the unitary notion of dissociation: disembodied but not embodied dissociative experiences are associated with exocentric perspective-taking

PubMed Central

Braithwaite, Jason J.; James, Kelly; Dewe, Hayley; Medford, Nick; Takahashi, Chie; Kessler, Klaus

2013-01-01

It has been argued that hallucinations which appear to involve shifts in egocentric perspective (e.g., the out-of-body experience, OBE) reflect specific biases in exocentric perspective-taking processes. Via a newly devised perspective-taking task, we examined whether such biases in perspective-taking were present in relation to specific dissociative anomalous body experiences (ABE) – namely the OBE. Participants also completed the Cambridge Depersonalization Scale (CDS; Sierra and Berrios, 2000) which provided measures of additional embodied ABE (unreality of self) and measures of derealization (unreality of surroundings). There were no reliable differences in the level of ABE, emotional numbing, and anomalies in sensory recall reported between the OBE and control group as measured by the corresponding CDS subscales. In contrast, the OBE group did provide significantly elevated measures of derealization (“alienation from surroundings” CDS subscale) relative to the control group. At the same time we also found that the OBE group was significantly more efficient at completing all aspects of the perspective-taking task relative to controls. Collectively, the current findings support fractionating the typically unitary notion of dissociation by proposing a distinction between embodied dissociative experiences and disembodied dissociative experiences – with only the latter being associated with exocentric perspective-taking mechanisms. Our findings – obtained with an ecologically valid task and a homogeneous OBE group – also call for a re-evaluation of the relationship between OBEs and perspective-taking in terms of facilitated disembodied experiences. PMID:24198776

Solvent-coordinate free-energy landscape view of water-mediated ion-pair dissociation

NASA Astrophysics Data System (ADS)

Yonetani, Yoshiteru

2017-12-01

Water-mediated ion-pair dissociation is studied by molecular dynamics simulations of NaCl in water. Multidimensional free-energy analysis clarifies the relation between two essential solvent coordinates: the water coordination number and water-bridge formation. These two are related in a complex way. Both are necessary to describe ion-pair dissociation. The mechanism constructed with both solvent variables clearly shows the individual roles. The water coordination number is critical for starting ion-pair dissociation. Water-bridge formation is also important because it increases the likelihood of ion-pair dissociation by reducing the dissociation free-energy barrier. Additional Ca-Cl and NH4-Cl calculations show that these conclusions are unaffected by changes in the ion charge and shape. The present results will contribute to future explorations of many other molecular events such as surface water exchange and protein-ligand dissociation because the same mechanism is involved in such events.

Monensin inhibits intracellular dissociation of asialoglycoproteins from their receptor

PubMed Central

1983-01-01

Treatment of short-term monolayer cultures of rat hepatocytes with the proton ionophore, monensin, abolishes asialoglycoprotein degradation, despite little effect of the drug on either surface binding of ligand or internalization of prebound ligand. Centrifuging cell homogenates on Percoll density gradients indicates that, as a result of monensin treatment, ligand does not enter lysosomes but sediments instead in a lower density subcellular fraction that is likely an endocytic vesicle. Analyzing the degree of receptor association of intracellular ligand revealed that monensin prevents the dissociation of the receptor-ligand complex that normally occurs subsequent to endocytosis. The weak base, chloroquine, also blocks this intracellular dissociation. Evidence from sequential substitution experiments is presented, indicating that monensin and chloroquine act at the same point in the sequence of events leading to ligand dissociation. These data are discussed in terms of a pH-mediated dissociation of the receptor-ligand complex within a prelysosomal endocytic vesicle. PMID:6304116

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.

Dissociative electron attachment to the radiosensitizing chemotherapeutic agent hydroxyurea

NASA Astrophysics Data System (ADS)

Huber, S. E.; Śmiałek, M. A.; Tanzer, K.; Denifl, S.

2016-06-01

Dissociative electron attachment to hydroxyurea was studied in the gas phase for electron energies ranging from zero to 9 eV in order to probe its radiosensitizing capabilities. The experiments were carried out using a hemispherical electron monochromator coupled with a quadrupole mass spectrometer. Diversified fragmentation of hydroxyurea was observed upon low energy electron attachment and here we highlight the major dissociation channels. Moreover, thermodynamic thresholds for various fragmentation reactions are reported to support the discussion of the experimental findings. The dominant dissociation channel, which was observed over a broad range of energies, is associated with formation of NCO-, water, and the amidogen (NH2) radical. The second and third most dominant dissociation channels are associated with formation of NCNH- and NHCONH2-, respectively, which are both directly related to formation of the highly reactive hydroxyl radical. Other ions observed with significant abundance in the mass spectra were NH2-/O-, OH-, CN-, HNOH-, NCONH2-, and ONHCONH2-.

Do dissociated or associated phoria predict the comfortable prism?

PubMed Central

Otto, Joanna M. N.; Kromeier, Miriam; Bach, Michael

2008-01-01

Background Dissociated and associated phoria are measures of latent strabismus under artificial viewing conditions. We examined to what extent dissociated and associated phoria predict the “comfortable prism”, i.e. the prism that appears most comfortable under natural viewing conditions. Methods For associated phoria, a configuration resembling the Mallett test was employed: both eyes were presented with a fixation cross, surrounded by fusionable objects. Nonius lines served as monocular markers. For dissociated phoria, the left eye was presented with all the Mallett elements, while only a white spot was presented to the right eye. To determine the comfortable prism, all the Mallett elements, including the Nonius lines, were shown to both eyes. In each of the three tests, the observer had to adjust a pair of counterrotating prisms. To avoid any (possibly prejudiced) influence of the experimenter, the prismatic power was recorded with a potentiometer. Twenty non-strabismic subjects with a visual acuity of ≥1.0 in each eye were examined. Results The range of the intertrial mean was for dissociated phoria from +9.3 eso to −5.9 cm/m exo, for associated phoria from +11.2 eso to −3.3 cm/m exo, and for the comfortable prism from +4.8 eso to −4.1 cm/m exo (cm/m = prism dioptre). In most observers, the phoria parameters differed greatly from the comfortable prism. On average, the phoria values were shifted about 2 cm/m towards the eso direction in relation to the comfortable prism (associated phoria not less than dissociated phoria). Conclusions The deviation of both, dissociated and associated phoria, from the comfortable prism suggests that the abnormal viewing conditions under which the phoria parameters are determined induce artefacts. Accordingly, the findings cast doubt on current textbook recommendations to use dissociated or associated phoria as a basis for therapeutic prisms. Rather, patients should be allowed to determine their comfortable prism

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. Copyright © 2014 Elsevier Inc. All rights reserved.

Dissociated emergent-response system and fine-processing system in human neural network and a heuristic neural architecture for autonomous humanoid robots.

PubMed

Yan, Xiaodan

2010-01-01

The current study investigated the functional connectivity of the primary sensory system with resting state fMRI and applied such knowledge into the design of the neural architecture of autonomous humanoid robots. Correlation and Granger causality analyses were utilized to reveal the functional connectivity patterns. Dissociation was within the primary sensory system, in that the olfactory cortex and the somatosensory cortex were strongly connected to the amygdala whereas the visual cortex and the auditory cortex were strongly connected with the frontal cortex. The posterior cingulate cortex (PCC) and the anterior cingulate cortex (ACC) were found to maintain constant communication with the primary sensory system, the frontal cortex, and the amygdala. Such neural architecture inspired the design of dissociated emergent-response system and fine-processing system in autonomous humanoid robots, with separate processing units and another consolidation center to coordinate the two systems. Such design can help autonomous robots to detect and respond quickly to danger, so as to maintain their sustainability and independence.

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.

Dissociation from beloved unhealthy brands decreases preference for and consumption of vegetables.

PubMed

Trump, Rebecca K; Connell, Paul M; Finkelstein, Stacey R

2015-09-01

Many people form strong bonds with brands, including those for unhealthy foods. Thus, prompting people to dissociate from beloved but unhealthy food brands is an intuitively appealing means to shift consumption away from unhealthy options and toward healthy options. Contrary to this position, we demonstrate that dissociating from unhealthy but beloved brands diminishes people's interest in consuming vegetables because the dissociation depletes self-regulatory resources. Across three experimental studies, we manipulate dissociation from two beloved brands both implicitly (studies 1-2) and explicitly (study 3) and observe effects on both preference for vegetables (studies 2-3) and actual vegetable consumption (study 1). In study 1, participants consumed fewer vegetables following dissociation from (vs. association with) a beloved candy brand. Study 2 demonstrates that the effect of depletion on preference for vegetables is more pronounced for those who strongly identify with the brand, as these individuals are most depleted by the dissociation attempt. Finally, study 3 illustrates that the difficulty experienced when trying to dissociate from beloved brands drives the observed effects on vegetable preference and consumption for those who strongly (vs. weakly) identify with the brand. Copyright © 2015 Elsevier Ltd. All rights reserved.

Psychological Dissection of Patients Having Dissociative Disorder: A Cross-sectional Study.

PubMed

Reddy, Lohit Somashekar; Patil, N M; Nayak, Raghavendra B; Chate, Sameeran S; Ansari, Saba

2018-01-01

Patients present with dissociative disorders as a decompensation to underlying stressful situation. It is clinically important to evaluate the presence, type, and temporal relation of the stressors resulting in dissociation. Further knowing the sociodemographic and psychological profile of the dissociative patient helps in better management. The study included 55 dissociative patients aged between 5 to 45 years. Psychiatric diagnosis was made using ICD-10 DCR. Psychosocial stressors and stressful life events were assessed using presumptive stressful life events scale/life events scale for Indian children and clinical interview. Personality and temperament traits were assessed using medico psychological questionnaire and temperament measurement schedule, respectively. Intelligence quotient (IQ) was assessed using standard progressive matrices and colored progressive matrices. Statistical analysis was done using Epi Info 7 software. All patients had significant psychosocial stressors preceding dissociation. Precipitating factor with temporal association was observed in only 83.64%. Family disharmony (41.82%) followed by education-related problems (29.09%) was the most common psychosocial stressors. 61.82% of the dissociative patients had psychiatric comorbidity. Mean IQ of study sample was 92.47. Dissociative children had high emotionality and energy levels but low sociability, rhythmicity, and distractibility. 50% of the adults were neurotic and had emotionally unstable personality. Dissociative disorders are commonly seen in females, adolescents, and in those from lower socioeconomic status and rural areas. They are always preceded by psychosocial stressors. Most of them have comorbid psychiatric disorders such as depression and anxiety. Neuroticism and emotionally unstable personality traits are common in adult patients while temperamental traits such as low sociability, low rhythmicity, low distractibility, high emotionality, and high energy levels are common in

Thermal regulation of methane hydrate dissociation: Implications for gas production models

USGS Publications Warehouse

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

2005-01-01

Thermal self-regulation of methane hydrate dissociation at pressure, temperature conditions along phase boundaries, illustrated by experiment in this report, is a significant effect with potential relevance to gas production from gas hydrate. In surroundings maintained at temperatures above the ice melting point, the temperature in the vicinity of dissociating methane hydrate will decrease because heat flow is insufficient to balance the heat absorbed by the endothermic reaction: CH4??nH2O (s) = CH4 (g) + nH2O (l). Temperature decreases until either all of the hydrate dissociates or a phase boundary is reached. At pressures above the quadruple point, the temperature-limiting phase boundary is that of the dissociation reaction itself. At lower pressures, the minimum temperature is limited by the H2O solid/liquid boundary. This change in the temperature-limiting phase boundary constrains the pressure, temperature conditions of the quadruple point for the CH4-H2O system to 2.55 ?? 0.02 MPa and 272.85 ?? 0.03 K. At pressures below the quadruple point, hydrate dissociation proceeds as the liquid H2O produced by dissociation freezes. In the laboratory experiments, dissociation is not impeded by the formation of ice byproduct per se; instead rates are proportional to the heat flow from the surroundings. This is in contrast to the extremely slow dissociation rates observed when surrounding temperatures are below the H2O solid/liquid boundary, where no liquid water is present. This "anomalous" or "self" preservation behavior, most pronounced near 268 K, cannot be accessed when surrounding temperatures are above the H2O solid/liquid boundary. ?? 2005 American Chemical Society.

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…

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…

The Dissociative Subtype of Post-traumatic Stress Disorder: Research Update on Clinical and Neurobiological Features.

PubMed

van Huijstee, Jytte; Vermetten, Eric

2017-10-21

Recently, a dissociative subtype of post-traumatic stress disorder (PTSD) has been included in the DSM-5. This review focuses on the clinical and neurobiological features that distinguish the dissociative subtype of PTSD from non-dissociative PTSD. Clinically, the dissociative subtype of PTSD is associated with high PTSD severity, predominance of derealization and depersonalization symptoms, a more significant history of early life trauma, and higher levels of comorbid psychiatric disorders. Furthermore, PTSD patients with dissociative symptoms exhibit different psychophysiological and neural responses to the recall of traumatic memories. While individuals with non-dissociative PTSD exhibit an increased heart rate, decreased activation of prefrontal regions, and increased activation of the amygdala in response to traumatic reminders, individuals with the dissociative subtype of PTSD show an opposite pattern. It has been proposed that dissociation is a regulatory strategy to restrain extreme arousal in PTSD through hyperinhibition of limbic regions. In this research update, promises and pitfalls in current research studies on the dissociative subtype of PTSD are listed. Inclusion of the dissociative subtype of PTSD in the DSM-5 stimulates research on the prevalence, symptomatology, and neurobiology of the dissociative subtype of PTSD and poses a challenge to improve treatment outcome in PTSD patients with dissociative symptoms.

Rate constants of agonist binding to muscarinic receptors in rat brain medulla. Evaluation by competition kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schreiber, G.; Henis, Y.I.; Sokolovsky, M.

The method of competition kinetics, which measures the binding kinetics of an unlabeled ligand through its effect on the binding kinetics of a labeled ligand, was employed to investigate the kinetics of muscarinic agonist binding to rat brain medulla pons homogenates. The agonists studied were acetylcholine, carbamylcholine, and oxotremorine, with N-methyl-4-(TH)piperidyl benzilate employed as the radiolabeled ligand. Our results suggested that the binding of muscarinic agonists to the high affinity sites is characterized by dissociation rate constants higher by 2 orders of magnitude than those of antagonists, with rather similar association rate constants. Our findings also suggest that isomerization ofmore » the muscarinic receptors following ligand binding is significant in the case of antagonists, but not of agonists. Moreover, it is demonstrated that in the medulla pons preparation, agonist-induced interconversion between high and low affinity bindings sites does not occur to an appreciable extent.« less

The dissociative chemisorption of CO2 on Ni(100): A quantum dynamics study

NASA Astrophysics Data System (ADS)

Farjamnia, Azar; Jackson, Bret

2017-02-01

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. Our computed dissociative sticking probabilities on Ni(100) for molecules in the ground state are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). We predict that the dissociative sticking behavior is similar on the two surfaces.

Factor structure and reliability of the Spanish version of the Dissociative Ability Scale.

PubMed

Pérez-Fabello, María José; Campos, Alfredo

2017-01-01

Everybody has dissociative ability to some extent, though this may vary from one individual to another. Several tests have been designed to measure dissociative ability, such as the Dissociative Ability Scale (Fisher, Johnson, & Elkins, 2013). Thus, the aim of this study was to assess the reliability and validity of the Spanish version of this test in a sample of 204 undergraduates seeking a fine arts degree at the University of Vigo (Spain). The reliability and validity of the Dissociative Ability Scale was found to be satisfactory for measuring dissociative ability. The results are discussed and innovative lines of research are proposed.

Parameterized cross sections for Coulomb dissociation in heavy-ion collisions

NASA Technical Reports Server (NTRS)

Norbury, John W.; Cucinotta, F. A.; Townsend, L. W.; Badavi, F. F.

1988-01-01

Simple parameterizations of Coulomb dissociation cross sections for use in heavy-ion transport calculations are presented and compared to available experimental dissociation data. The agreement between calculation and experiment is satisfactory considering the simplicity of the calculations.

X-ray structural studies of quinone reductase 2 nanomolar range inhibitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pegan, Scott D.; Sturdy, Megan; Ferry, Gilles

Quinone reductase 2 (QR2) is one of two members comprising the mammalian quinone reductase family of enzymes responsible for performing FAD mediated reductions of quinone substrates. In contrast to quinone reductase 1 (QR1) which uses NAD(P)H as its co-substrate, QR2 utilizes a rare group of hydride donors, N-methyl or N-ribosyl nicotinamide. Several studies have linked QR2 to the generation of quinone free radicals, several neuronal degenerative diseases, and cancer. QR2 has been also identified as the third melatonin receptor (MT3) through in cellulo and in vitro inhibition of QR2 by traditional MT3 ligands, and through recent X-ray structures of humanmore » QR2 (hQR2) in complex with melatonin and 2-iodomelatonin. Several MT3 specific ligands have been developed that exhibit both potent in cellulo inhibition of hQR2 nanomolar, affinity for MT3. The potency of these ligands suggest their use as molecular probes for hQR2. However, no definitive correlation between traditionally obtained MT3 ligand affinity and hQR2 inhibition exists limiting our understanding of how these ligands are accommodated in the hQR2 active site. To obtain a clearer relationship between the structures of developed MT3 ligands and their inhibitory properties, in cellulo and in vitro IC{sub 50} values were determined for a representative set of MT3 ligands (MCA-NAT, 2-I-MCANAT, prazosin, S26695, S32797, and S29434). Furthermore, X-ray structures for each of these ligands in complex with hQR2 were determined allowing for a structural evaluation of the binding modes of these ligands in relation to the potency of MT3 ligands.« less

Sensory dissociation in chronic low back pain: Two case reports.

PubMed

Adamczyk, Wacław M; Luedtke, Kerstin; Saulicz, Oskar; Saulicz, Edward

2018-08-01

Patients with chronic low back pain often report that they do not perceive their painful back accurately. Previous studies confirmed that sensory dissociation and/or discrepancy between perceived body image and actual size is one of the specific traits of patients with chronic pain. Current approaches for measuring sensory dissociation are limited to two-point-discrimination or rely on pain drawings not allowing for quantitative analysis. This case study reports the sensory dissociation of two cases with chronic low back pain using a recently published test (point-to-point-test (PTP)) and a newly developed test (two-point-estimation (TPE)). Both patients mislocalized tactile stimuli delivered to the painful location compared to non-painful locations (PTP test). In addition, both patients perceived their painful lumbar region differently from non-painful sites above and below and contralateral to the painful site. TPE data showed two distinct clinical patterns of sensory dissociation: one patient perceived the two-point distance in the painful area as expanded, while the other patient perceived it as shrunk. The latter pattern of sensory dissociation (i.e., pattern shrunk) is likely to respond to sensory training. Whether enlarged patterns of sensory dissociation are more resistant to treatment remains unknown but would explain the low effectiveness of previous studies using sensory training in chronic low back pain populations. Subgrouping patients according to their sensory discrimination pattern could contribute to the choice and effectiveness of the treatment approach.

Self-reports of trauma and dissociation: An examination of context effects.

PubMed

Lemons, Peter; Lynn, Steven Jay

2016-08-01

To examine context effects in moderating the link between self-reported trauma and dissociation in undergraduate samples, we administered these measures either in the same or different experimental contexts. Trauma History Screen/THS (Carlson et al., 2011)-Dissociative Experiences Scale/DES-II (Bernstein & Putnam, 1986) correlations revealed a context effect (greater correlations in same test context), although multiple regression analyses did not confirm this finding. A context effect was supported in DES-Taxon scores using multiple regression for the THS but not the Modified Posttraumatic Stress Scale (MPSS-SR; Falsetti, Resnick, Resick, & Kilpatrick, 1993), an effect confirmed with correlation comparisons. Ethnicity influenced the association between measures of trauma and dissociation. Overall, the relation between measures of trauma and dissociation was small to medium, although high correlations were observed between the DES depersonalization/derealization subscale and the Multiscale Dissociation Inventory (Briere, Weathers, & Runtz, 2005) depersonalization and derealization subscales, supporting the construct validity of these measures. Copyright © 2016 Elsevier Inc. All rights reserved.

Psychological Dissection of Patients Having Dissociative Disorder: A Cross-sectional Study

PubMed Central

Reddy, Lohit Somashekar; Patil, N. M.; Nayak, Raghavendra B.; Chate, Sameeran S.; Ansari, Saba

2018-01-01

Background: Patients present with dissociative disorders as a decompensation to underlying stressful situation. It is clinically important to evaluate the presence, type, and temporal relation of the stressors resulting in dissociation. Further knowing the sociodemographic and psychological profile of the dissociative patient helps in better management. Materials and Methods: The study included 55 dissociative patients aged between 5 to 45 years. Psychiatric diagnosis was made using ICD-10 DCR. Psychosocial stressors and stressful life events were assessed using presumptive stressful life events scale/life events scale for Indian children and clinical interview. Personality and temperament traits were assessed using medico psychological questionnaire and temperament measurement schedule, respectively. Intelligence quotient (IQ) was assessed using standard progressive matrices and colored progressive matrices. Statistical analysis was done using Epi Info 7 software. Results: All patients had significant psychosocial stressors preceding dissociation. Precipitating factor with temporal association was observed in only 83.64%. Family disharmony (41.82%) followed by education-related problems (29.09%) was the most common psychosocial stressors. 61.82% of the dissociative patients had psychiatric comorbidity. Mean IQ of study sample was 92.47. Dissociative children had high emotionality and energy levels but low sociability, rhythmicity, and distractibility. 50% of the adults were neurotic and had emotionally unstable personality. Conclusion: Dissociative disorders are commonly seen in females, adolescents, and in those from lower socioeconomic status and rural areas. They are always preceded by psychosocial stressors. Most of them have comorbid psychiatric disorders such as depression and anxiety. Neuroticism and emotionally unstable personality traits are common in adult patients while temperamental traits such as low sociability, low rhythmicity, low distractibility

A general mechanism for competitor-induced dissociation of molecular complexes

PubMed Central