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In order to deliver effective care, it is necessary to organise interdisciplinary activities for older persons who suffer from depressive disorders. This paper evaluated the interdisciplinary team members' perceptions of cooperation in the discharge planning of depressed older persons based on the Chronic Care Model (CCM). A qualitative implementation design was used, data were collected by means of multistage focus groups, and a thematic analysis was performed. Three themes emerged: lack of effective team leadership in the community, the need to change the delivery system, and enhancing self-management support for depressed older persons as well as the participation of their families. It was concluded that nurse managers must find ways of supporting the depressed older persons by better structuring the care, increasing cooperation with organisational leadership, and creating an environment characterised by trust and mutual respect. Distrust can have serious implications for discharge planning collaboration. The development of a common vision of transparency in the organization is important as is a policy of change among leadership and in clinical practice.

Depression is a socially- and physically-disabling condition. The Chronic Care Model (CCM) was developed to promote better management of long-term conditions, such as depression, in primary care settings. The aim of the study was to identify barriers to, and facilitators of, success when implementing the CCM for the management of depression in primary care. A systematic search was conducted in electronic databases from January 2005 to December 2011. Thirteen articles met the inclusion criteria and were reviewed by means of a thematic analysis. The barriers were categorized under two themes: lack of organizational, administrative, and professional ability to change and implement the components of the CCM; and lack of clarity pertaining to the responsibility inherent in the role of care manager (often a nurse) when it comes to promoting the patient's self-management ability. In terms of the facilitators of success, two themes emerged: leadership support and vision, and redesigning the delivery system. When shaping an environment for organizational change, leadership and professionals must work towards a common goal and vision. Such processes require a care manager with a clear role and responsibilities in order for the health-care system to meet the needs of the person with depression., (© 2012 The Authors. International Journal of Mental Health Nursing © 2012 Australian College of Mental Health Nurses Inc.)

Aim: To explore home-care nurses' experiences of patient safety in their delivery of home care to older clients., Background: High-risk organisations, such as the airline industry and the petroleum industry, have long been preoccupied with safety. Only recently has this also become a central theme in health care., Method: Four focus group interviews with 20 nurses who work in home care. A qualitative thematic analysis was performed., Results: One main theme was identified: struggling with responsibility in different situations. It comprises five subthemes: poor work morale and work ethic; documentation; lack of functional leadership; competence; and lack of updated routines and guidelines., Conclusions: Patient safety culture is compromised by a lack of leadership, lack of responsibility among leadership, lack of routines, failure to update procedures, and a lack of knowledge and education among health-care workers., Implications for Nursing Management: Nurse managers need to be made more aware of the dilemmas faced by nurses, how they struggle with their responsibilities, how they experience powerlessness in certain situations, and the lack of support they receive in decision-making., (© 2012 Blackwell Publishing Ltd.)

Aim: To evaluate the benefits of self-management interventions on the quality of life of patients with chronic obstructive pulmonary disease., Background: Chronic obstructive pulmonary disease is one of the most widespread chronic conditions worldwide, and it is predicted to increase over the next decade. Although previous review studies have demonstrated the benefits of self-management interventions on health-care utilisation, their benefits on quality of life are still unclear., Method: In this systematic review, we examined four randomised controlled trials undertaken between 2000 and 2011 to evaluate the benefits of chronic obstructive pulmonary disease self-management interventions on patient quality of life., Results: The main theme that emerged was that self-management interventions improved patient well-being, with three minor themes: reducing the burden on patients, improved patient activity and improved total patient health., Conclusion: Self-management interventions tend to improve the quality of life of patients with chronic obstructive pulmonary disease. Further randomised controlled trials are recommended to evaluate self-management interventions in chronic obstructive pulmonary disease to confirm these benefits., Implications for Nursing Management: Nursing management in health services is involved in caring for patients with chronic obstructive pulmonary disease and is responsible for liaising with other members of the health-care team. We recommend that nursing management be engaged in health-care services to develop and implement self-management interventions for chronic obstructive pulmonary disease patients to improve their quality of life., (© 2012 Blackwell Publishing Ltd.)

Here, we present synchrotron radiation circular dichroism spectra for a series of DNA adenine strands, (dA)(n) , n = 2-10, 15, at acidic pH. Reference spectra of a protonated single strand, (dAH(+) )(n) , and a protonated double helix, (dAH(+) )(n) :(dAH(+) )(n) , are provided in the wavelength region from 175 to 330 nm. The largest spectral difference between single and double strands is in the vacuum ultraviolet, where a band changes sign. This new spectral feature that characterizes double helix formation may be useful for analytical purposes but also for shedding light on the underlying complexation mechanism. Furthermore, we find that a minimum of eight or nine bases in a strand is needed for two (dAH(+) )(n) strands to form a duplex. This is a relatively high number as compared with guanine quadruplex and cytosine i-motif formation, which is likely linked to the significant Coulomb repulsion between the all-protonated bases. Finally, spectra recorded as a function of time after sample preparation indicates that the equilibrium is slowly reached, in certain cases taking an hour or more., (Copyright © 2012 Wiley Periodicals, Inc.)

The death of a partner in later life is generally experienced as the most stressful normative life event. This study reviewed evidence about the emotional state of widows. Both qualitative and quantitative studies were included in the review. A systematic search was made of the OVID Medline, PubMed, ProQuest, and EBSCOhost/Academic Search Premier databases using the following search words: "depression", "elderly"/"older", "emotional state", "mood", "self-management", "widows", and "women" for the period January 2000 to December 2010. Thirteen articles met the inclusion criteria, and a qualitative content analysis was used to review them. The findings revealed one main theme: "A struggle to perceive meaning in the meaningless", which was based on three themes: "Numbing the pain and struggling to control feelings", "Feeling sad, yet trying to maintain close emotional relationships and meaningful activities", and "The process of change and self-management dominated by resilience". The widows seemed overwhelmed by the need to overcome an unbearable emotional state. The resilience process was experienced as a struggle, and they required time to improve their well-being and self-management. To achieve self-management, nurses should strengthen widows' optimism, control, well-being, and the pathways that lead to recovery., (© 2012 Blackwell Publishing Asia Pty Ltd.)

Borderline personality disorder (BPD) is described as the most lethal of psychiatric disorders, with suicide rates of 3-9.5%, a rate almost 50 times higher than that of the general population. The struggle to recover by changing suicidal behaviour is not well described in relation to people with BPD. The most common reason given for suicide attempts was to escape or obtain relief from situations of extreme distress. The aim of this study was to explore how a recovery process facilitated changes in suicidal behaviour in a sample of women with BPD. An exploratory design was used. Data were collected by means of in-depth interviews (n = 13), and a thematic analysis was employed. The findings revealed two themes: 'struggling to assume responsibility for self and others' and 'struggling to stay alive by enhancing self-development'. The first theme comprised three subthemes: 'the desire to recover by searching for strength', 'the struggle to be understood as the person you are', and 'recovering by refusing to be violated'. The second theme comprised one subtheme: 'recovering by feeling safe and trusted'. The main finding of this study suggests that women with BPD who exhibit suicidal behaviour can change when they feel confirmed, safe, and trusted., (© 2011 The Authors. International Journal of Mental Health Nursing © 2011 Australian College of Mental Health Nurses Inc.)

Purpose: Patients with a history of allergic reaction to penicillin, but with no detectable specific IgE, are common and pose a dilemma. Challenge tests are considered to be the diagnostic gold standard. The aim of this study was to identify subgroups of patients with very low risk for reactions who could be safely tested using a more rapid and simple procedure., Methods: A total of 580 consecutively referred adult patients with a history of non-serious cutaneous allergic reactions to penicillin, but with no IgE, were challenged with therapeutic doses of penicillin V (phenoxymethylpenicillin), penicillin G (benzylpenicillin), or both., Results: Only 14 of 580 patients had a positive challenge test. In 11 of the 14, a reaction to challenge occurred within 2 hours, and none were anaphylactic. The year of the original reaction was known for 555 patients; a positive challenge was seen in only 0.4% of those with an original reaction >15 years before challenge, but in 4.6% of those with a more recent original reaction (P=0.001). Onset of a reaction within the first day of the original exposure was a predictive factor for a positive challenge (P=0.001) in patients challenged within 15 years of the original reaction., Conclusions: Among suspected penicillin-allergic patients with non-severe skin reactions and no detectable specific IgE, the subgroup of patients who originally reacted more than 15 years previously had very low risk for reacting to a challenge. The risk was higher in patients with a more recent original reaction, especially if the symptoms had occurred within the first day of exposure.

Circular dichroism (CD) is a powerful technique to obtain information on electronic transitions and has been used extensively for studies on DNA. Most experiments are done in the UV region but new information is often revealed from extending the wavelength region down into the vacuum ultraviolet (VUV) region. Such experiments are most easily carried out with synchrotron radiation (SR) light sources that provide large photon fluxes. Here we provide a summary of the SRCD data taken on different DNA strands with emphasis on results from our own laboratory within the last five years.(1-3) Signal intensities in the VUV are often significantly larger than those in the UV, and the electronic coupling between bases may increase with excitation energy. CD spectroscopy is particularly useful for investigating the extent of electronic coupling within a strand, i.e., the degree of delocalisation of the excited-state electronic wavefunction. The spatial extent of the wavefunction may be limited to just one base or it extends over two or more bases in a stack or between bases on different strands.(4,5) The actual character of the electronically excited state is linked to base composition and sequence as well as DNA folding motif (A-, B-, Z-DNA, triplexes, quadruplexes, etc.). The latter depends on experimental conditions such as solution acidity, temperature, ionic strength, and solvent.

Electron-transfer and -capture dissociations of doubly protonated peptides gave dramatically different product ions for a series of histidine-containing pentapeptides of both non-tryptic (AAHAL, AHAAL, AHADL, AHDAL) and tryptic (AAAHK, AAHAK, AHAAK, HAAAK, AAAHR, AAHAR, AHAAR, HAAAR) type. Electron transfer from gaseous Cs atoms and fluoranthene anions triggered backbone dissociations of all four N-C(alpha) bonds in the peptide ions in addition to loss of H and NH(3). Substantial fractions of charge-reduced cation-radicals did not dissociate on an experimental time scale ranging from 10(-6) to 10(-1) s. Multistage tandem mass spectrometric (MS(n)) experiments indicated that the non-dissociating cation-radicals had undergone rearrangements. These were explained as being due to proton migrations from N-terminal ammonium and COOH groups to the C-2' position of the reduced His ring, resulting in substantial radical stabilization. Ab initio calculations revealed that the charge-reduced cation-radicals can exist as low-energy zwitterionic amide pi* states which were local energy minima. These states underwent facile exothermic proton migrations to form aminoketyl radical intermediates, whereas direct N-C(alpha) bond cleavage in zwitterions was disfavored. RRKM analysis indicated that backbone N-C(alpha) bond cleavages did not occur competitively from a single charge-reduced precursor. Rather, these bond cleavages proceeded from distinct intermediates which originated from different electronic states accessed by electron transfer. In stark contrast to electron transfer, capture of a free electron by the peptide ions mainly induced radical dissociations of the charge-carrying side chains and loss of a hydrogen atom followed by standard backbone dissociations of even-electron ions. The differences in dissociation are explained by different electronic states being accessed upon electron transfer and capture.

Here we report synchrotron radiation circular dichroism spectra of various G-quadruplexes from 179 to 350 nm, and a number of bands in the vacuum ultraviolet (VUV) are reported for the first time. For a tetramolecular parallel structure, the strongest band in the spectrum is a negative band in the VUV at 182 nm; for a bimolecular antiparallel structure with diagonal loops, a new strong positive band is found at 190 nm; for a bimolecular parallel structure with edgewise loops, a strong positive band at 189 nm is observed; and for a self-folded chair-type structure, the strongest band in the spectrum is a positive band at 187 nm. For the tetramolecular parallel structure, the CD signals at all wavelengths are dominated by contributions from quartets of G bases, and the signal strength is approximately proportional to the number of quartets. Our experiments on well-characterized G-quadruplex structures lead us to question past attributions of CD signals to helix handedness and G quartet polarity. Although differences can be observed in the VUV region for the various quadruplex types, there do not appear to be clear-cut spectral features that can be used to identify specific topological features. It is suggested that this is because a dominant positive band in the VUV seen near 190 nm in all quadruplex structures is due to intrastrand guanine-guanine base stacking. However, our spectra can serve as reference spectra for the G-quadruplex structures investigated and, not least, to benchmark theoretical calculations and empirical models.

Aim: The aim of the present study was to illuminate what the mental health nursing (MHN) leader needs in order to develop her/his leadership role., Background: MHN leadership has tended to focus on the nature of the care provided rather than the development of the role., Method: This literature review (1998-2008) examines papers from the past decade by means of a synthesis of empirical studies., Results: Three themes emerged: * clarifying role expectations and areas for development at the same time as increasing the influence on patients with mental health problems; * using evidence-based practice to implement improvements and organizational change in mental health; and * employing communication skills as well as supporting, nurturing and empowering others., Conclusion: This review provided evidence that the MHN leader needs various skills in order to make enlightened changes that can meet the needs of both patients and staff., Implications for Nursing Management: The MHN leader needs to explore the range of tasks involved in leadership in order to define role expectations and areas for development. These areas include enhancing patient care; reliance on team work; and attending to the personal life of the staff; increasing collaboration within the organization as well as with the community; utilizing the best available evidence; and communicating in order to improve the organization.

In this work we have recorded synchrotron radiation circular dichroism (SRCD) spectra from 180 nm to 360 nm of cytosine strands [(dC)(n), n = 1, 2, ..., 10] in aqueous solution at different pH values to reveal electronic coupling between bases in different ionisation states. The geometry of the strands is determined by the pH value and the strand length and the local organisation of the cytosines will determine the base-to-base interaction that impacts on the CD signal. At low pH where all bases are protonated, there is no signature of electronic coupling between the bases, and the SRCD spectrum is simply n times that of the n = 1 spectrum. At higher pH where all bases are neutral, the spectra for n > 1 differ from the monomer spectrum, which implies electronic coupling between bases. The correlation between the CD signal and n is linear, and the spatial extent of the excited state wavefunction is therefore over just two stacked bases both in the UV and VUV. At intermediate pH, the low-n spectra are different from the high-n spectra, and a transition is seen to occur at n = 6-8. We ascribe this behavior to the formation of i-motif structures between four (dC)(n) strands for high n.

The aim of this study was to explore and interpret women's desire to survive emotional pain related to self-harm. Women who suffer from borderline personality disorder describe emotional pain as intense. Previous research indicates that self-harm is a way of obtaining emotional relief and offers an escape from unwanted emotions, thoughts, and/or distressing situations. An explorative, interpretative design was employed. The data were collected by means of in-depth interviews with a sample of women resident in Norway suffering from borderline personality disorder and were analyzed using a hermeneutic approach. The findings revealed one main theme, self-sacrifice, and two other themes, self-harm (a struggle to be relieved of responsibility) and a fear of intimacy versus intrusion. This study indicates that self-sacrifice appears to imply a longing for reconnection with the self and others. To preserve their self-image, the women require courage to survive the painful state of unworthiness.

Transition metal cations Co2+, Ni2+ and Zn2+ form 1 : 1 : 1 ternary complexes with 2,2'-bipyridine (bpy) and peptides in aqueous methanol solutions that have been studied for tripeptides GGG and GGL. Electrospray ionization of these solutions produced singly charged [Metal(bpy)(peptide-H)]+ and doubly charged [Metal(bpy)(peptide)]2+ ions (Metal = metal ion) that underwent charge reduction by glancing collisions with Cs atoms at 50 and 100 keV collision energies. Electron transfer to [Metal(bpy)(peptide)]2+ ions was less than 4.2 eV exoergic and formed abundant fractions of non-dissociated charge-reduced intermediates. Charge-reduced [Metal(bpy)(peptide)]+ ions dissociated by the loss of a hydrogen atom, ammonia, water and ligands that depended on the metal ion. The Ni and Co complexes mainly dissociated by the elimination of ammonia, water, and the peptide ligand. The Zn complex dissociated by the elimination of ammonia and bpy. A sequence-specific fragment was observed only for the Co complex. Electron transfer to [Metal(bpy)(peptide-H)]+ was 0.6-1.6 eV exoergic and formed intermediate radicals that were detected as stable anions after a second electron transfer from Cs. [Metal(bpy)(peptide-H)] neutrals and their anions dissociated by the loss of bpy and peptide ligands with branching ratios that depended on the metal ion. Optimized structures for several spin states, electron transfer and dissociation energies were addressed by combined density functional theory and Møller-Plesset perturbational calculations to aid interpretation of experimental data. The experimentally observed ligand loss and backbone cleavage in charge-reduced [Metal(bpy)(peptide)]+ complexes correlated with the dissociation energies at the present level of theory. The ligand loss in +CR- spectra showed overlap of dissociations in charge-reduced [Metal(bpy)(peptide-H)] complexes and their anionic counterparts which complicated spectra interpretation and correlation with calculated dissociation energies., (Copyright 2009 John Wiley & Sons, Ltd.)

Here we report on the charge partition between c and z fragments formed after femtosecond collisional electron-transfer from Cs atoms to charge-tagged peptide dications. Peptides chosen for study were Ala-Lys (AK) and Lys-Lys (KK) where one or both of the lysine epsilon-amino groups were trimethylated to provide one or two fixed charges. For peptides with only one charge tag, the other charge was obtained by protonation of an amino group. In some experiments the ammonium group was tagged by 18-crown-6-ether (CE). Since recombination energies decrease in the order: MeNH3+ > NMe4+ > MeNH3+(CE) > NMe4+(CE), it is possible to change the probability for the transferred electron to end up at either the N-terminal or the C-terminal residue by CE attachment. We find, however, that the individual recombination energies have little influence on the relative ratio between the yield of c and z ions as long as there are no mobile protons that can be transferred between the two fragments. Our results can be accounted for by the Utah-Washington model where the electron is captured into an amide pi* orbital that weakens the N-C(alpha) bond and causes its breakage, followed by proton, electron, or hydrogen transfer between the c and z fragments that stay together as an ion-molecule complex for some time. The data are also in accordance with the notion that an amide group competes with the charged groups for the electron. Electron capture by charged groups results in loss of small neutrals such as hydrogen and ammonia.

The aim of this study was to explore the way in which traumatic childhood experiences influenced the daily life of women with Borderline Personality Disorder (BPD). An explorative design comprising in-depth interviews and a qualitative content analysis was used. The findings revealed one main theme-Longing for Reconciliation-comprising two themes: (1) Living with a sense of shame and guilt and (2) Struggling to be released from a sense of being trapped. Longing for reconciliation influenced the women's daily life as well as their search for the meaning of traumatic childhood experiences. New meaning can emerge through change, forgiveness, and reconciliation, thus helping women with BPD overcome their struggle and gain the insight and strength to look into their secret knowledge. Meaning can emerge and help them to develop an empathic understanding of themselves in the context of past and present relationships.

Synchrotron radiation circular dichroism (SRCD) spectra were recorded for a family of 12 DNA duplexes that all contain nine adenines (A) and nine thymines (T) in each strand but in different combinations. The total number of AT Watson-Crick (WC) base pairs is constant (18), but the number of cross-strand (CS) hydrogen bonds between A and T varies between 0 and 16, the maximum possible. Eleven of the duplexes have one or more A tracts, and one duplex has T tracts. The signals due to hybridization were found from subtraction of spectra of single strands from spectra of the duplexes. The residual spectrum of the T-tract duplex T(9)A(9):A(9)T(9) (5'-3':3'-5') significantly differs from that of the A-tract duplex A(9)T(9):T(9)A(9), but only below 210 nm, which suggests that the signal in this region depends on the superhelicity of the duplex. A principal component analysis of all residual spectra reveals that spectra of A-tract duplexes can be obtained to a good approximation as a linear combination of just two basis spectra. The first component is assigned to the spectrum of 18 WC and 8 CS pairs, whereas the second component is that of 8 CS pairs. This interpretation is supported by separate experiments on duplexes of varying lengths but with similar arrangements of the A and T's and by experiments on two other duplex families of 14 and 30 base pairs. The best correlation is obtained by the assumption that cross-strand interactions occur as long as there are two adenine neighbors in a strand. Our data indicate that a circular dichroism spectrum of a duplex containing only A and T can simply be inferred from the number of WC base pairs and the number of CS interactions, and we provide reference spectra for these two interactions. Finally, time dependent density functional theory calculations of the circular dichroism spectra for an isolated WC base pair and two different CS base pairs (between adenine N-6 amine and thymine O-4 or between adenine C-2-H and thymine O-2) were performed to provide some additional support for the interpretation of the experimental spectra. We find large differences between the two calculated CS spectra. However, there is a reasonable qualitative agreement between the calculated WC and the C-2-H...O-2 CS spectra and those deduced from the experimental data.

The results from an experimental study of bare and microsolvated peptide monocations in high-energy collisions with cesium vapor are reported. Neutral radicals form after electron capture from cesium, which decay by H loss, NH(3) loss, or N-C(alpha) bond cleavage into characteristic z(*) and c fragments. The neutral fragments are converted into negatively charged species in a second collision with cesium and are identified by means of mass spectrometry. For protonated GA (G = glycine, A = alanine), the branching ratio between NH(3) loss and N-C(alpha) bond cleavage is found to strongly depend on the molecule attached (H(2)O, CH(3)CN, CH(3)OH, and 18-crown-6 ether (CE)). Addition of H(2)O and CH(3)OH increases this ratio whereas CH(3)CN and CE decrease it. For protonated AAA ([AAA+H](+)), a similar effect is observed with methanol, while the ratio between the z(1) and z(2) fragment peaks remains unchanged for the bare and microsolvated species. Density functional theory calculations reveal that in the case of [GA+H](+)(CE), the singly occupied molecular orbital is located mainly on the amide group in accordance with the experimental results.

Electron-induced dissociations of gas-phase ternary copper-2,2'-bipyridine complexes of Gly-Gly-Gly and Gly-Gly-Leu were studied on a time scale ranging from 130 ns to several milliseconds using a combination of charge-reversal ((+)CR(-)) and electron-capture-induced dissociation (ECID) measured on a beam instrument and electron capture dissociation (ECD) measured in a Penning trap. Charge-reduced intermediates were observed on the short time scale in the (+)CR(-) and ECID experiments but not in ECD. Ion dissociations following electron transfer or capture mostly occurred by competitive bpy or peptide ligand loss, whereas peptide backbone fragmentations were suppressed in the presence of the ligated metal ion. Extensive electron structure theory calculations using density functional theory and large basis sets provided optimized structures and energies for the precursor ions, charge-reduced intermediates, and dissociation products. The Cu complexes underwent substantial structure changes upon electron capture. Cu was calculated to be pentacoordinated in the most stable singly charged complexes of the [Cu(peptide-H)bpy](+*) type where it carried a approximately +1 atomic charge. Cu coordination in charge-reduced [Cu(peptide-H)bpy] intermediates depended on the spin state. The themodynamically more stable singlet states had tricoordinated Cu, whereas triplet states had a tetracoordinated Cu. Cu was tricoordinated in stable [Cu(peptide-H)bpy](-*) products of electron transfer. [Cu(peptide)bpy](2+*) complexes contained the peptide ligand in a zwitterionic form while Cu was tetracoordinated. Upon electron capture, Cu was tri- or tetracoordinated in the [Cu(peptide)bpy](+) charge-reduced analogs and the peptide ligands underwent prototropic isomerization to canonical forms. The role of excited singlet and triplet electronic states is assessed., (2009 John Wiley & Sons, Ltd.)

A gaseous nanocalorimetry approach is used to investigate effects of hydration and ion identity on the energy resulting from ion-electron recombination. Capture of a thermally generated electron by a hydrated multivalent ion results in either loss of a H atom accompanied by water loss or exclusively loss of water. The energy resulting from electron capture by the precursor is obtained from the extent of water loss. Results for large-size-selected clusters of Co(NH(3))(6)(H(2)O)(n3)(+) and Cu(H(2)O)(n2)(+) indicate that the ion in the cluster is reduced on electron capture. The trend in the data for Co(NH(3))(6)(H(2)O)(n3)(+) over the largest sizes (n >/= 50) can be fit to that predicted by the Born solvation model. This agreement indicates that the decrease in water loss for these larger clusters is predominantly due to ion solvation that can be accounted for by using a model with bulk properties. In contrast, results for Ca(H(2)O)(n2)(+) indicate that an ion-electron pair is formed when clusters with more than approximately 20 water molecules are reduced. For clusters with n = approximately 20-47, these results suggest that the electron is located near the surface, but a structural transition to a more highly solvated electron is indicated for n = 47-62 by the constant recombination energy. These results suggest that an estimate of the adiabatic electron affinity of water could be obtained from measurements of even larger clusters in which an electron is fully solvated.

The effects of water on electron capture dissociation products, molecular survival, and recombination energy are investigated for diprotonated Lys-Tyr-Lys solvated by between zero and 25 water molecules. For peptide ions with between 12 and 25 water molecules attached, electron capture results in a narrow distribution of product ions corresponding to primarily the loss of 10-12 water molecules from the reduced precursor. From these data, the recombination energy (RE) is determined to be equal to the energy that is lost by evaporating on average 10.7 water molecules, or 4.3 eV. Because water stabilizes ions, this value is a lower limit to the RE of the unsolvated ion, but it indicates that the majority of the available RE is deposited into internal modes of the peptide ion. Plotting the fragment ion abundances for ions formed from precursors with fewer than 11 water molecules as a function of hydration extent results in an energy resolved breakdown curve from which the appearance energies of the b 2 (+), y 2 (+), z 2 (+*), c 2 (+), and (KYK + H) (+) fragment ions formed from this peptide ion can be obtained; these values are 78, 88, 42, 11, and 9 kcal/mol, respectively. The propensity for H atom loss and ammonia loss from the precursor changes dramatically with the extent of hydration, and this change in reactivity can be directly attributed to a "caging" effect by the water molecules. These are the first experimental measurements of the RE and appearance energies of fragment ions due to electron capture dissociation of a multiply charged peptide. This novel ion nanocalorimetry technique can be applied more generally to other exothermic reactions that are not readily accessible to investigation by more conventional thermochemical methods.

Ion nanocalorimetry is used to measure the effects of electron kinetic energy in electron capture dissociation (ECD). With ion nanocalorimetry, the internal energy deposited into a hydrated cluster upon activation can be determined from the number of water molecules that evaporate. Varying the heated cathode potential from -1.3 to -2.0 V during ECD has no effect on the average number of water molecules lost from the reduced clusters of either [Ca(H2O)15]2+ or [Ca(H2O)32]2+, even when these data are extrapolated to a cathode potential of zero volts. These results indicate that the initial electron kinetic energy does not go into internal energy in these ions upon ECD. No effects of ion heating from inelastic ion-electron collisions are observed for electron irradiation times up to 200 ms, although some heating occurs for [Ca(H2O)17]2+ at longer irradiation times. In contrast, this effect is negligible for [Ca(H2O)32]2+, a cluster size typically used in nanocalorimetry experiments, indicating that energy transfer from inelastic ion-electron collisions is negligible compared with effects of radiative absorption and emission for these larger clusters. These results have significance toward establishing the accuracy with which electrochemical redox potentials, measured on an absolute basis in the gas phase using ion nanocalorimetry, can be related to relative potentials measured in solution.

A new method for time-resolved daughter ion mass spectrometry is presented, based on the electrostatic ion storage ring in Aarhus, ELISA. Ions with high internal energy, e.g., as a result of photoexcitation, dissociate and the yield of neutrals is monitored as a function of time. This gives information on lifetimes in the microsecond to millisecond time range but no information on the fragment masses. To determine the dissociation channels, we have introduced pulsed supplies with switching times of a few microseconds. This allows rapid switching from storage of parent ions to storage of daughter ions, which are dumped into a detector after a number of revolutions in the ring. A fragment mass spectrum is obtained by monitoring the daughter ion signal as a function of the ring voltages. This technique allows identification of the dissociation channels and determination of the time dependent competition between these channels.

This paper presents a synthesis of content and assessment of the methodological rigour of published literature related to concepts of emotional pain and distress in women with a diagnosis of borderline personality disorder (BPD). In the past two decades, there has been an increase in research about the prevalence of BPD, interventions, and relative effectiveness of various forms of treatment. However, there are few studies regarding emotional pain and distress in women with BPD. Emotional pain has been reported as an adaptive response to repetitive traumatic experiences in childhood. Searches of the EBSCO host, OVID MEDLINE, CINAHL, and PsycINFO databases were carried out using the following search words: borderline personality disorder, emotional pain, distress, self, suffering, women, for the period 1996-2006. Fifteen papers were assessed for methodological rigour, followed by the analysis of the concepts of emotional pain and distress. Three themes emerged from the literature, the emotionally abused and neglected child; struggling with emotions leading to self-injury; and social problems related to difficulties regulating emotions. A high prevalence of reported childhood abuse was revealed. Emotional pain was described as intense for women suffering from BPD. A further synthesis of research findings is recommended to provide information on the effectiveness of interventions.

Circular dichroism (CD) experiments on DNA single strands (dA(n)) at the ASTRID synchrotron radiation facility reveal that eight adenine (A) bases electronically couple upon 190 nm excitation. After n=8, the CD signal increases linearly with n with a slope equal to the sum of the coupling terms. Nearest neighbor interactions account for only 24% of the CD signal whereas electronic communication is limited to nearest neighbors for two other exciton bands observed at 218 and 251 nm (i.e., dimer excited states). Electronic coupling between bases in DNA is important for nonradiative deexcitation of electronically excited states since the hazardous energy is spread over a larger spatial region.

15N-labeling of di- and tripeptides reveals that electron capture to doubly protonated peptides results almost exclusively in ammonia loss from the N-terminal end, which clearly shows that a significant fraction of electron capture occurs at this end. In accordance with this finding, the competing channel of N-Calpha bond breakage leads to z+* ions and neutral c fragments after electron capture to small dications. In larger peptides that live long enough for internal proton exchanges to occur, c+ ions are also formed and in some cases in dominant yield. Attachment of one or two crown ethers to ammonium groups is likely to reduce the probability of proton transfer, which enhances the formation of z+* relative to c+. The total yield of z+* and c+ is, however, more or less unchanged, which indicates that proton transfer or hydrogen transfer from a NH3 group to the amide group is not required for the N-Calpha bond breakage.

We have developed an experimental technique that allows us to study the physics of short lived molecular dianions in the gas phase. It is based on the formation of monoanions via electrospray ionization, acceleration of these ions to keV energies, and subsequent electron capture in a sodium vapor cell. The dianions are stored in an electrostatic ion storage ring in which they circulate with revolution times on the order of 100 micros. This enables lifetime studies in a time regime covering five orders of magnitude, 10(-5)-1 s. We have produced dianions of 7,7,8,8-tetracyano-p-quinodimethane and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane (TCNQ-F(4)) and measured their lifetimes with respect to electron autodetachment. Our data indicate that most of the dianions were initially formed in electronically excited states in the electron transfer process. Two levels of excitation were identified by spectroscopy on the dianion of TCNQ-F(4), and the absorption spectrum was compared with spectra obtained from spectroelectrochemistry of TCNQ-F(4) in acetonitrile solution.

Electron capture by both bare and microsolvated small peptide dications was investigated by colliding these ions with sodium vapor in an accelerator mass spectrometer to provide insight into processes that occur on the microsecond time frame. Survival of the intact peptide monocation after electron capture depends strongly on molecular size. For dipeptides, no intact reduced species were observed; the predominant ions correspond to loss of hydrogen and ammonia. In contrast, the intact reduced species was observed for larger peptides. Calculated structures indicate that the diprotonated dipeptide ions form largely extended structures with low probability of internal ionic hydrogen bonding (i.e., charge solvation) whereas internal ionic H-bonding occurs extensively for larger peptide dications. Solvation of the peptide ions with between one to seven methanol molecules reduces the total extent of H loss even for dipeptides where intact reduced species can survive more than a microsecond after electron capture. The yield of ions corresponding to cleavage of NCalpha bonds (c+ and z+* ions) does not depend strongly on peptide size but decreases with the extent of microsolvation for the dipeptide dications. H-bonding appears to play an important role for the survival of the intact reduced ions but less so for the formation of c+ and z+* ions. Our results indicate that electron capture predominantly occurs at the ammonium groups (at least 70 to 80%), and provides important new insights into the electron capture dissociation process.

Objective: To determine the quantitative and qualitative antibody responses to a pneumococcal conjugate vaccine (PnCV) in human immunodeficiency virus (HIV)-exposed infected and uninfected children., Methods: Children were randomized to receive either a PnCV or placebo at 6, 10 and 14 weeks of age. PnCV serotype-specific antibody concentrations were measured by a standard enzyme immunoassay (EIA) and a 22F modified EIA (22F EIA) on single serum samples drawn at 21-42 days post-dose 3. Functional activities of the serotype-specific antibody to serotypes 6B, 19F and 23F were measured with an opsonophagocytic assay (OPA)., Results: The geometric mean antibody concentrations (GMC) were similar in HIV-infected and HIV-uninfected PnCV recipients for 7 of the 9 vaccine serotypes. In placebo recipients, the GMCs were significantly higher in HIV-infected than in uninfected children for 7 of the serotypes. In HIV-infected PnCV recipients, the GMCs were lower for 5 of the serotypes in children with severe acquired immunodeficiency syndrome than in children who were asymptomatic or mildly symptomatic with acquired immunodeficiency syndrome. HIV-infected PnCV recipients were less likely to have measurable functional antibody (OPA titer > or =1/8) to all 3 studied serotypes (6B, 19F and 23F) than in HIV-uninfected children. HIV-infected children required a higher concentration of anticapsular antibody to achieve 50% of the maximum uptake of labeled Streptococcus pneumoniae in the OPA assay than HIV-uninfected children for 2 of the 3 serotypes, although this was significant only for serotype 6B (P = 0.0005)., Conclusion: HIV-infected children have similar quantitative antibody responses but poorer qualitative antibody responses to the PnCV.

Insulin-like growth factor (IGF)-I is essential for cerebellar granule neuron survival and a decline in IGF-I is implicated in various age-dependent processes. Here we show that IGF-I mRNA levels are decreased in the cerebellum of old rats compared with young rats and this was associated with increased cell death and activation of caspases 3 and 9. Growth hormone-releasing peptide (GHRP)-6, a synthetic ligand for the ghrelin receptor, increased IGF-I mRNA levels, decreased cell death and inhibited caspase 3 and 9 activation in the cerebellum of aged rats. These results suggest that increasing IGF-I expression in the cerebellum can decrease cell death in aged rats via inhibition of caspase 3 and 9 activation.