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PubMed1990

Rates of dissociation of sex steroid hormones from human sex hormone-binding globulin: a reassessment.

A rapid filtration assay employing dextran-coated charcoal as acceptor particles for free hormone was used to measure the rates of dissociation of dihydrotestosterone (DHT), testosterone (T), and estradiol (E2) from their binding proteins in human serum at 37 degrees C. Because measurements were begun after each hormone had fully (greater than 99%) dissociated from albumin, the observed rates of dissociation correspond to the rates of dissociation of the sex hormone-binding globulin (SHBG)-hormone complexes. The dissociation rate constants of the hormone-SHBG complexes were determined to be 0.016 +/- 0.001, 0.056 +/- 0.002, and 0.083 +/- 0.003 s-1 for DHT, T, and E2, respectively, corresponding to half-times of dissociation (t1/2) of 43, 12 and 8.4 s, respectively. The physiological significance of these findings can best be appreciated by comparing these t1/2 s with the capillary and sinusoidal transit times of various tissues (less than 1 s to approximately 10 s).

Dihydrotestosterone↗
PubMed2006

Stochastic approaches to understanding dissociations in inflectional morphology.

Computer modelling research has undermined the view that double dissociations in behaviour are sufficient to infer separability in the cognitive mechanisms underlying those behaviours. However, all these models employ multi-modal representational schemes, where functional specialisation of processing emerges from the training process. Targeted lesioning of different regions of functional specialisation leads to varied but predictable deficits in model performance. We argue that multi-modal representational schemes are not a necessary condition for the observation of double dissociations in an information processing system that shares resources across multiple tasks. Using a uni-modal representational system, we demonstrate that double dissociations may also result from stochastic processes. Lesioning experiments on a single-route, uni-modal connectionist model of regular and irregular noun and verb morphology confirm and extend earlier work demonstrating that selective impairment across tasks can result from damage to a distributed information processing system. A systematic investigation of the degree to which performance deteriorates across different inflectional classes reveals that simple and double dissociations can occur in this single-route, uni-modal model. An important prediction of the model is that double dissociations between regular and irregular inflection, resulting from stochastic processes should be extremely rare. However, they are particularly likely to occur when the researcher uses test batteries consisting of a small number of items. Given that cognitive neuropsychologists rarely provide details about the distribution of performance in a disordered population, it is concluded that a stochastic interpretation of double dissociations may have wider applicability than is normally supposed.

Alzheimer Disease↗
PubMed2006

Comparing mono- and divalent DNA groove binding cyanine dyes -- binding geometries, dissociation rates, and fluorescence properties.

The unsymmetrical cyanine dyes BOXTO-PRO and BOXTO-MEE were derived from the DNA groove binder BOXTO, by adding a positively charged or a non-ionic hydrophilic tail to BOXTO, respectively. The main objective was to obtain more efficient DNA probes, for instance in electrophoresis and microscopy, by slowing down the dissociation of BOXTO from DNA. The interactions with mixed sequence DNA was studied with fluorescence and absorbance spectroscopy, stopped-flow dissociation and gel electrophoresis. Both the derivatives are groove bound as BOXTO, and have similar fluorescence properties when bound to mixed sequence DNA in free solution. BOXTO-PRO exhibits a slower dissociation than BOXTO from DNA, whereas the dissociation rate for BOXTO-MEE is faster and, unexpectedly independent of the ionic strength. During gel electrophoresis both BOXTO-PRO and BOXTO-MEE exhibit a faster dissociation rate than BOXTO. Still, BOXTO-PRO seems to be a good alternative as DNA probe, especially for applications in free solution where the dissociation is slower than for the corresponding intercalator TOPRO-1.

Binding Sites↗
PubMed2005

Dissociation enzyme effects on the potassium currents of inner hair cells isolated from guinea-pig cochlea.

Tetraethylammonium (TEA)-sensitive potassium currents in the cochlear inner hair cells (IHCs) possess the kinetics of fast inactivation. Some enzymes using for IHCs dissociation affect these inactivation kinetics. IHCs were dissociated from guinea-pig cochlea by 1 mg/ml trypsin or 0.25 mg/ml protease VIII, and the properties of the K+ currents were compared using conventional whole-cell voltage-clamp recordings. TEA-sensitive potassium currents showed fast inactivation kinetics in both trypsin-dissociated cells and protease VIII-dissociated cells. The time constant of the inactivation phase in trypsin-treated cells was similar to that in protease VIII-treated cells. However, the rate of inactivation (compared by the ratio between the steady-state current and initial peak current) in protease VIII-treated cells was larger than that in trypsin-treated cells. In protease VIII-dissociated cells, the time constant of recovery from inactivation elucidated by paired-pulse protocol was 3.5 ms. Papain is another enzyme that is sometimes used for dissociating IHCs, so effects of papain were observed. Extracellular papain application (8 unit/ml) demonstrated a slight increase of the outward potassium currents.

Animals↗
PubMed2006

Dissociated hypotropia: clinical features and surgical management of two cases.

BACKGROUND: Dissociated vertical deviation (DVD), which almost always shows a hypertropia of the affected eye, occasionally can manifest as a hypotropia, either unilaterally or bilaterally. Two patients are presented who had this rare variant of DVD, which has been termed "dissociated hypotropia," both of whom underwent surgery and had good outcomes. METHODS: Two patients, ages 13 and 14, with unilateral dissociated hypotropia underwent large inferior rectus muscle recessions on their affected eyes. In one case, a video-based eye tracker was used to record the dissociated hypotropic drifts in the eye to plot the changes in the drift amplitudes in response to increasing density filters over the fixating eye (Bielschowsky phenomenon) and to confirm whether the deviation changed in the light versus the dark. RESULTS: In case 1, the hypotropia drift measured up to 18(Delta), and it was reduced to zero with a 6 mm inferior rectus recession in the affected eye. In case 2, the drift measured up to 20(Delta). Eye movement recordings showed a time course of the downward drift that mirrored that of upward drift of hypertropic DVD and confirmed the presence of a Bielschowsky phenomenon. The drift amplitude did not change in bright versus dark conditions. An 8 mm inferior rectus recession on the affected eye reduced the hypotropia to 5(Delta). CONCLUSIONS: Dissociated hypotropia is a rare form of the dissociated strabismus complex. The downward drift has a time course similar to the upward drift of hypertropic DVD and shows the Bielschowsky phenomenon. It responds to a large inferior rectus muscle recession.

Adolescent↗
PubMed2004

Chiral recognition of zinc(II) ion complexes composed of bicyclo[3.3.0] octane-2,6-diol and s-naproxen probed by collisional-induced dissociation.

Chiral recognition of racemic bicyclo[3.3.0] octane-2,6-diol(B) was achieved in the gas phase using s-Naproxen(A) as reference, using the kinetics of competitive unimolecule dissociation of tetrameric zinc(II)-bound complexes by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometer(ESI-FTMS). As undergoing a mild competitive collision-induced dissociation(CID) experiment with a constant pressure argon gas introduced by leak valve, the tetrameric cluster ion [A(2)B(2)Z(n)(II)-H](+) forms only two trimeric ions and R(chiral) is subsequently obtained in the kinetic method. Further studies obtained the difference of Gibbs free energy of [ABZ(n)(II)-H](+)(Delta Delta G(ABZn(II)-H](+))) by dissociating [A(2)BZ(n)(II)-H](+), resulting two fragment ions [ABZ(n)(II)-H](+) and [A(2)Z(n)(II)-H](+), which can be established to a linear relationship between Delta Delta G([ABZn(II)-H](+)) and R(chiral)' basing on the kinetic method. The value of R(chiral)' suggested that Delta Delta G([ABZn(II)-H](+)) could be regarded as zero. Meanwhile, dissociation of [AB(2)Z(n)(II)-H](+) generated only one daughter ion [ABZ(n)(II)-H](+) in a stable pressure. Thus, a linear relationship was established between the difference of Gibbs free energy of [AB(2)Z(n)(II)-H](+)(Delta Delta G([AB(2)Zn(II)-H](+))) and R(chiral)" if the Delta Delta G([ABZn(II)-H](+)) can be negligible. Because there is also a linear relationship of R(chiral) in the tetrameric ion [A(2)B(2)Z(n)(II)-H](+) and the Gibbs energy difference of trimeric cluster ion [A(2)BZ(n)(+)(II)-H](Delta Delta G([A(2)BZn(II)-H](+))) plus that of [AB(2)Z(n)(II)-H](+), Delta Delta G([A(2)BZ(n)(II)-H]+]) is easy to be calculated in the dissociation process of tetrameric ion. Stable of R(chiral), R(chiral)' and R(chiral)" under different pressures show T(eff) does not affect the chiral recognition of cluster ions in the condition selected. If an only-one-daughter-ion fragment process of [A(2)BZ(n)(II)-H](+) was existed, R(chiral)''' relating to this dissociation would be calculated just like R(chiral)" of [AB(2)Z(n)(II)-H](+) does. Conclusion was obtained that [A(2)BZ(n)(II)-H](+) makes more contribution to chiral recognition of tetrameric ion measured by kinetic method than [AB(2)Z(n)(II)-H](+) does as R(chiral)''' and R(chiral)" were applied as index to evaluate the Gibbs free energy difference of these two trimeric cluster ions. Further discussion shows that steric interactions and pi-pi stacking interactions are the major factors responsible for the observed efficient chiral recognition in this system.

Anti-Inflammatory Agents, Non-Steroidal↗
PubMed2005

Protonated adenine: tautomers, solvated clusters, and dissociation mechanisms.

Ab initio and density functional theory calculations at the B3-MP2 and CCSD(T)/6-311 + G(3df,2p) levels of theory are reported that address the protonation of adenine in the gas phase, water clusters, and bulk aqueous solution. The calculations point to N-1-protonated adenine (1+) as the thermodynamically most stable cationic tautomer in the gas phase, water clusters, and bulk solution. This strongly indicates that electrospray ionization of adenine solutions produces tautomer 1+ with a specificity calculated as 97-90% in the 298-473 K temperature range. The mechanisms for elimination of hydrogen atoms and ammonia from 1+ have also been studied computationally. Ion 1+ is calculated to undergo fast migrations of protons among positions N-1, C-2, N-3, N-10, N-7, and C-8 that result in an exchange of five hydrogens before loss of a hydrogen atom forming adenine cation radical at 415 kJ mol(-1) dissociation threshold energy. The elimination of ammonia is found to be substantially endothermic requiring 376-380 kJ mol(-1) at the dissociation threshold and depending on the dissociation pathway. The overall dissociation is slowed by the involvement of ion-molecule complexes along the dissociation pathways. The competing isomerization of 1+ proceeds by a sequence of ring opening, internal rotations, imine flipping, ring closures, and proton migrations to effectively exchange the N-1 and N-10 atoms in 1+, so that either can be eliminated as ammonia. This mechanism explains the previous N-1/N-10 exchange upon collision-induced dissociation of protonated adenine.

Adenine↗
PubMed2006

Development of new screening system for Alzheimer disease, in vitro Abeta sink assay, to identify the dissociation of soluble Abeta from fibrils.

Abeta is one of the primary therapeutic targets for Alzheimer disease (AD). Abeta vaccination induces the disappearance of Abeta deposits. Since few reports have focused on the reverse phase of Abeta aggregation, we established a new screening system, the in vitro Abeta sink assay, to clarify the process of dissociation of soluble forms from fibrils. Abeta42 was more resistant to dissociation from fibrils to monomers and/or low molecular weight (LMW) soluble oligomers than Abeta40. We applied this system to find a potential therapy for AD. Ultrasound irradiation significantly enhanced the dissociation of soluble Abeta from fibrils, while ultrasound experiments also confirmed the difference between Abeta40 and Abeta42. We found that some compounds enhanced the dissociation of Abeta from fibrils. Here, we proposed that Abeta42 was more resistant to dissociation from fibrils to monomers and/or LMW soluble oligomers than Abeta40, and this system might be useful to identify dissociation of soluble Abeta from fibrils.

Alzheimer Disease↗
PubMed2002

Trait dissociation affects the behavioral response to cholecystokinin tetrapeptide in healthy man.

Trait dissociation might influence the response to panicogens in normal controls. The behavioral effects of 25 microg of cholecystokinin tetrapeptide (CCK-4) were studied in 18 healthy men, nine each with high or low trait dissociation. Subjects with high trait dissociation showed a significantly lower increase of acute dissociative, anxiety and panic symptoms compared with subjects with low trait dissociation. Trait dissociation should be assessed in further behavioral challenge studies as a potentially important covariate.

Adult↗
PubMed1997

Dissociation equilibria of the tryptophan synthase alpha 2 beta 2 complex in saline buffer and guanidine isothiocyanate, as studied by sedimentation equilibrium.

The dissociation equilibria of Salmonella typhimurium tryptophan synthase alpha 2 beta 2 complex were studied via centrifugation of the complex to sedimentation equilibrium in neutral saline buffers containing 0 to 137 mM guanidine isothiocyanate (GuSCN). The resulting concentration gradients were analyzed in the context of an equilibrium model for sequential dissociation of two alpha subunits from a stable beta 2 subunit. Under the conditions of these experiments, the first dissociation constant alone could be evaluated at GuSCN concentrations < or = 100 mM, and the second dissociation constant alone could be evaluated at GuSCN = 137 mM. At intermediate GuSCN, both dissociation constants were sufficiently well defined to rule out the presence of a large equilibrium cooperative effect in the stepwise dissociation of the alpha subunits.

Bacterial Proteins↗
PubMed1997

Regulation of the priming of exocytosis and the dissociation of SNAP-25 and VAMP-2 in adrenal chromaffin cells.

The MgATP-dependent priming step of exocytosis has been suggested to be regulated negatively by GTP-binding protein G0 in permeabilized adrenal chromaffin cells. We have reported that synaptosomal-associated protein of 25 kDa (SNAP-25) and vesicle-associated membrane protein 2 (VAMP-2) form a complex in chromaffin cells, and the complex dissociates during MgATP-dependent priming. In this study, we examined whether G0 controls such dissociation of the SNAP-25/VAMP-2 complex in the regulation of priming. In digitonin-permeabilized cells, MgATP-gamma-S which can be a phosphate donor for protein phosphorylation failed to cause priming and dissociation of the SNAP-25/VAMP-2 complex. Mastoparan, which directly activates G0, selectively inhibited priming and blocked dissociation of the SNAP-25/VAMP-2 complex. These results suggest that ATP hydrolysis and dissociation of the SNAP-25/VAMP-2 complex are responsible for priming. These results also suggest that dissociation of the complex is one of the sequential steps for priming controlled by G0.

Adenosine Triphosphate↗
PubMed1996

Can cast immobilization successfully treat scapholunate dissociation associated with distal radius fractures?

During a 3.5-year period, 20 of 424 consecutive patients with fractures of the distal radius presented with evidence of scapholunate dissociation upon x-ray films and traction view fluoroscopy. The sequential changes of x-ray abnormalities of the scapholunate joint were consistently observed over a 1-year period, and wrist functions were evaluated 1 year after injury. The scapholunate gaps were 3.5 +/- 0.5 mm at the time of injury, 3.2 +/- 0.4 mm immediately after closed reduction of the fracture, 3.4 +/- 0.5 mm at the time after removal of fixation, and 3.8 +/- 0.4 mm 1 year after injury. By the modified clinical scoring system of Green and O'Brien, of these 20 patients, none had excellent, 2 had good, 14 had fair, and 4 had poor wrist function 1 year after injury. The wrists with scapholunate dissociation had significantly worse function as compared to a selected subgroup of 228 wrists with no signs of intercarpal ligament disruption. All 20 patients with signs of scapholunate dissociation on x-ray examination at the time of injury had clinical signs in the scapholunate joint and positive x-rays findings of dissociation 1 year later. After 1 year, 8 of the 20 patients underwent surgery for relief of symptoms and to stabilize the joint. Arthrography in the patients with persistent symptoms showed disruption in scapholunate interosseous ligaments. This study indicates that scapholunate dissociation with concomitant fractures of the distal radius cannot be cured by cast immobilization of the fracture. Early operative treatment should be instituted for the concomitant scapholunate dissociation.

Adult↗
PubMed2000

Measurement of collision-induced dissociation rates for tantalum oxide ions in a quadrupole ion trap.

A study of factors influencing the collision-induced dissociation (CID) rate of strongly bound diatomic ions effected via resonance excitation in a quadrupole ion trap is presented. From these studies, an approach to measuring the CID rates is described wherein product ion recovery is optimized and the effect of competitive processes (e.g., parent ion ejection and product ion reactions) on rate measurements are prevented from influencing rate measurements. Tantalum oxide ions (dissociation energy = 8.2 eV), used as a model system, were formed via reactions of glow discharge generated Ta+ ions with residual gases in the ion trap. Neon (0.5 mtorr) was found to be a more favorable target gas for the dissociation of TaO+ than He and Ar, but collisional activation of TaO+ ions in neon during ion isolation by mass selective instability necessitated ion cooling prior to dissociation. A 25 ms delay time at qz = 0.2 allowed for kinetic cooling of stored TaO+ ions and enabled precise dissociation rate measurements to be made. CID of TaO+ was determined to be most efficient at qz = 0.67 (226 kHz for m/z 197). Suitable resonance excitation voltages and times ranged from 0.56 to 1.2 V(p-p) and 1 to 68 ms, respectively. Under these conditions, measurement of rates approaching 80 s(-1) for the dissociation of TaO+ could be made without significant complications associated with competing processes, such as ion ejection.

Journal Article↗
PubMed2002

Thermal dissociation of the protein homodimer ecotin in the gas phase.

The influence of charge on the thermal dissociation of gaseous, protonated, homodimeric, protein ecotin ions produced by nanoflow electrospray ionization (nanoES) was investigated using the blackbody infrared radiative dissociation technique. Dissociation of the protonated dimer, (E2 + nH)(n+) congruent to E2(n+) where n = 14-17, into pairs of monomer ions is the dominant reaction at temperatures from 126 to 175 degrees C. The monomer pair corresponding to the most symmetric charge distribution is preferred, although 50-60% of the monomer product ions correspond to an asymmetric partitioning of charge. The relative abundance of the different monomer ion pairs produced from E2(14+), E2(15+), and E2(16+) depends on reaction time, with the more symmetric charge distribution pair dominating at longer times. The relative yield of monomer ions observed late in the reaction is independent of temperature indicating that proton transfer between the monomers does not occur during dissociation and that the different monomer ion pairs are formed from dimer ions which differ in the distribution of charge between the monomers. For E2(17+), the yield of monomer ions is independent of reaction time but does exhibit slight temperature dependence, with higher temperatures favoring the monomers corresponding to most symmetric charge distribution. The charge distribution in the E2(15+) and E2(16+) dimer ions influences the dissociation kinetics, with the more asymmetric distribution resulting in greater reactivity. In contrast, the charge distribution has no measurable effect on the dissociation kinetics and energetics of the E2(17+) dimer.

Bacterial Proteins↗
PubMed2003

Evaluation of noncovalent interactions between peptides and polyether compounds via energy-variable collisionally activated dissociation.

Energy-variable collisionally activated dissociation (CAD) was used to analyze noncovalent interactions of protonated peptide/polyether complexes in a quadrupole ion trap complexes were formed with a series of four polyether host molecules and thirteen peptide molecules. Comparison of dissociation thresholds revealed correlations between the gas-phase basicities of the peptides and polyether molecules and the onset of dissociation. The dissociation thresholds of complexes containing the tripeptides or pentapeptides were inversely proportional to the gas-phase basicities of the sites of protonation of the peptides. Intramolecular hydrogen bonding of the pentapeptides affected the observed dissociation thresholds as well. The dissociation thresholds also scaled proportionally to the gas-phase basicities of the polyethers in the complexes, and the importance of the conformational flexibility of the polyether ligand was confirmed for one of the histidine-containing tripeptide complexes.

Amino Acid Sequence↗
PubMed1998

Dissociative phenomena in congenital monocular elevation deficiency.

INTRODUCTION: 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. METHODS: 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. RESULTS: 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. CONCLUSION: The current study demonstrates that dissociated vertical deviation occurs in association with monocular elevation deficiency.

Aging↗
PubMed1997

[Rheologic study of the dissociation reaction of erythrocyte immunologic agglutinates: application to subgroup A erythrocytes].

Red blood cell Agglutinates can be dissociated by providing enough energy which may be supplied by shear stress in a viscometer. In this paper a new technique is proposed to determine dissociation parameters of erythrocyte immunological agglutinates by using a laser backscattering method. Backscattered light intensity increases during the process of agglutinate dissociation when a controlled shear stress in a transparent Couette viscometer is applied. The obtained curves of dissociation can be fitted by an exponential function. A numerical integration of the dissociation curves allows us to obtain a parameter associated to the energy used in the dissociation process. A satisfactory differentiation of erythrocyte sub-groups Al, Az, A,B and Am has been carried out using this technique.

Blood Viscosity↗
PubMed1994

Infrared multiphoton dissociation of large multiply charged ions for biomolecule sequencing.

Characterization and verification of the structures of large biomolecules with high-resolution tandem Fourier transform mass spectrometry with electrospray ionization is critically dependent on the technique used to fragment the multiply charged ions produced. Infrared multiphoton dissociation (IRMPD) of ionized proteins as large as carbonic anhydrase (29 kDa) yields fragment information similar to, but with valuable additions to, that of other dissociation techniques. IRMPD yields product ions on-axis, providing efficient dissociation in further stages; MS3 of ubiquitin (8.6 kDa) yields 11 new sequence ions. Optimum irradiation times for protein ion dissociation vary by more than a factor of 6, with times for oligonucleotides far lower, possibly due to photon resonance with a P-O stretching frequency. IRMPD provides far greater selectivity than collisionally activated dissociation and also appears to yield much less mass discrimination and to dissociate much more stable ions. A technique to remove product ions on formation from the laser beam should improve the present efficiencies of 30-80%.

Animals↗