Kinetically Trapped Liquid-State Conformers of a Sodiated Model Peptide Observed in the Gas Phase

We investigate the peptide AcPheAla5LysH+, a model system for studying helix formation in the gas phase, in order to fully understand the forces that stabilize the helical structure. In particular, we address the question of whether the local fixation of the positive charge at the peptide's C-terminus is a prerequisite for forming helices by replacing the protonated C-terminal Lys residue by Ala and a sodium cation. The combination of gas-phase vibrational spectroscopy of cryogenically cooled ions with molecular simulations based on density-functional theory (DFT) allows for detailed structure elucidation. For sodiated AcPheAla6, we find globular rather than helical structures, as the mobile positive charge strongly interacts with the peptide backbone and disrupts secondary structure formation. Interestingly, the global minimum structure from simulation is not present in the experiment. We interpret that this is due to high barriers involved in re-arranging the peptide-cation interaction that ultimately result in kinetically trapped structures being observed in the experiment.Comment: 28 pages, 10 figure

US-Pakistan Strategic Partnership: A Track II Dialogue

"The Center on Contemporary Conflict (CCC), with support from the Defense Threat Reduction Agency (DTRA), held the sixth iteration of the U.S.-Pakistan Strategic Dialogue (Track II) on September 18-19, 2011 in Phuket, Thailand. The dialogue was held in partnership with and through the local support of the Institute for Security and International Studies (ISIS). Like all five past dialogues, the aim was to draw upon the core themes from the current regional and strategic climate with explicit focus on strategic stability in the region. The expected outcome will possibly inform official discussions in both countries, especially for those who are involved in policymaking and implementation. Once again, like the previous iterations, this dialogue brought together top American and Pakistani scholars, former officials, and observers to address the very important strategic issues that affect the relationship between the two countries and suggest pathways for resolving these issues. The panels arranged in this year's agenda sparked in-depth and frank discussions on a variety of security issues. The first day was organized to discuss overall U.S.-Pakistan Relations and Strategic Balancing in South Asia. The second day focused solely on Deterrence Stability in South Asia with a specific focus on the impact of military modernizations, including: the nuclear and conventional fields, the potential introduction of tactical nuclear weapons (TNW), and new technologies in the complex strategic environment of South Asia."2012 002Approved for public release; distribution is unlimited

LTLf and LDLf Monitoring: A Technical Report

Runtime monitoring is one of the central tasks to provide operational decision support to running business processes, and check on-the-fly whether they comply with constraints and rules. We study runtime monitoring of properties expressed in LTL on finite traces (LTLf) and in its extension LDLf. LDLf is a powerful logic that captures all monadic second order logic on finite traces, which is obtained by combining regular expressions and LTLf, adopting the syntax of propositional dynamic logic (PDL). Interestingly, in spite of its greater expressivity, LDLf has exactly the same computational complexity of LTLf. We show that LDLf is able to capture, in the logic itself, not only the constraints to be monitored, but also the de-facto standard RV-LTL monitors. This makes it possible to declaratively capture monitoring metaconstraints, and check them by relying on usual logical services instead of ad-hoc algorithms. This, in turn, enables to flexibly monitor constraints depending on the monitoring state of other constraints, e.g., "compensation" constraints that are only checked when others are detected to be violated. In addition, we devise a direct translation of LDLf formulas into nondeterministic automata, avoiding to detour to Buechi automata or alternating automata, and we use it to implement a monitoring plug-in for the PROM suite

Cryogenic Ion Spectroscopy of Peptides and Glycans

Understanding the structure of biomolecules, which are directly related to physiological processes that take place in the human body, has always generated a large interest in the scientific community. In this thesis we focus our attention on two of these classes of biomolecules: peptides and glycans. In the first part of this work we investigate how the structure of helical peptides in the gas-phase is modified when one increases the number of amino acids in the sequence. Moreover, we analyze the role played by a mobile charge in the formation of the helical motif in the gas-phase. To achieve these goals, we make use of a home-built tandem mass spectrometer, and a pump-probe laser spectroscopic scheme. The combination of infrared and ultraviolet light together with cryogenic temperatures allows one to collect high-resolution conformer-specific spectra of gas-phase peptides. By comparing the experimental results obtained with density functional theory calculations, we show that the synergy between theory and experiment is key to provide accurate structural characterization of the investigated peptides. The mobile charge, in fact, induces unconventional backbone conformations, which cannot be predicted a priori by performing experiments alone. In the second part of this thesis we present a novel technique to identify and characterize glycans in the gas-phase that exploits a database approach. Due to their structural heterogeneity, glycans pose a problem for the currently available mass- and mobility-spectrometry techniques. In the work herein we show that we can easily identify glycan structural isomers, by adding a spectroscopic dimension to mass and mobility measurements. Cryogenic vibrational messenger spectroscopy, in fact, allows us to unambiguously identify disaccharides and pentasaccharides isomers due to the high-resolution provided by this method. Moreover, we can perform our experiments in a broad range of temperatures, going from liquid helium to liquid nitrogen. This shows the potential of our technique in becoming a more accessible analytical tool for glycan identification

GEOGRAFIE DEL VINO: COSTRUZIONE STORICA E PATRIMONIALIZZAZIONE DEI PAESAGGI VITICOLI

This research project is supposed to face up viticulture in a complex, epistemological framework. As Dickenson and Salt affirm the geography of the wine \uabmay be studied from a variety of perspectives and encompasses the influence of the physical environment, historical diffusion of the vine and viticulture, economic geographies of cultivation and marketing, political influences on trade and production, and cultural perceptions of landscapes, product and people\ubb. After all, already in the Latin etymology of viticulture exists a deep content hiatus that imposes to consider two fair enough different concepts; indeed, culture may refer to cultivation and care. Therefore, it is crucial to understand how viticulture must be considered and to show the way its dichotomic nature may suggest distant methodologies of investigation. After having underlined the epistemological framework of viticulture in relationship to geography and given the interpretative tools of the research, I analyzed the construction and the evolution of some viticultural landscapes (Montalcino, Barolo, Bolgheri and the C\uf4te d\u2019Or) whose choice depends on the dynamics that regarded their production (characterized by a particular propensity to commercialization), the relationships and the differences among them and finally the essential relationship that wine creates with its territory of origin. The role of the tradition represents the fil rouge that links these experiences and it declines in a different perspective according to the realities I analyzed. However, for each of them, it has been fundamental the role developed by a forerunner; indeed, Ferruccio Biondi for Brunello di Montalcino, Juliette Colbert-Falletti for Barolo and Mario Incisa della Rocchetta for the Sassicaia have not only contributed to the creation of a wine but generally to the development of a whole territory that is identified today in the cultivation of the grapevine. Finally, in virtue of such a rooted and shared historical construction, these territories take part in the processes of patrimonialization that are characterizing some wine regions to a global scale. Following different criterions of classification, where however viticulture covers a preponderant aspect, Val d\u2019Orcia, Langhes and the climats de Bourgogne are considered from the UNESCO a human world heritage to safeguard while Bolgheri has been inserted by Regione Tuscana in the catalog of the historical rural landscapes; in all these cases, independently from who promoted the patrimonialization, the aim is clear: to allow the future generations to enjoy the cultural and environmental wealth that distinguish them. The wine landscapes are reported to be the ones that underwent fast and important transformations. Moving from this, I underline the debate around the relationship between patrimonialization (considered as a specific process of conservation) and the general transformation of the landscape. From this perspective, the criterions of patrimonialization adopted for the viticultural landscapes seem not to consider the eventuality of one change in the case wine shouldn\u2019t play the social and economic role that it has nowadays. What would it happen in that case

Gynecological surgical interventions (conservative and non-conservative): Clinical psychological variables and symptomatology pertaining to perioperative period

Objective: After considering great inter-individual variability of subjective experience and clinical course in reference to conservative and non-conservative gynecological surgical interventions, an attempt was made to evaluate potential role of several clinical and psychological variables with respect to perioperative symptomatology course and illness behaviour. Materials and methods: The sample consists of 58 women (mean age 41.4 ± 8.7) undergoing gynecological surgical interventions (conservative and non-conservative ones) for benign pathologies. The anamnestic and clinical data (psychological anamnesis, clinical history, indications, methods and typology of the intervention) were collected using a specifically designed summary form. For the evaluation of pre-and post-operative symptomatology course and illness behaviour, the following psychological tests were respectively used: The Symptom Questionnaire (SQ), with 3 planned administrations (respectively 15 days before the intervention, a day before the intervention and at discharge) and the Illness Behavior Questionnaire (IBQ), completed before discharge. Non-parametric tests (Mann-Whitney and Kruskal-Wallis) were used to compare performances on independent samples. Results: Results show that perioperative course and illness behaviour in the cases of gynecological surgical interventions for benign pathologies depend on clinical variables, that is, typology and methods of the intervention, clinical history, psychopathological anamnesis. Conclusion: Findings suggest the importance of clinical-anamnestic inquiry oriented towards the evaluation of variables that emerged as risk factors, with the goal of planning personalized support interventions for preventing and/or reducing distress and impact on psychophysical wellbeing arising after gynaecological surgical interventions

Strategies for Psychiatric Rehabilitation and their Cognitive Outcomes in Schizophrenia: Review of Last Five-year Studies

Background: Cognitive deficits are core features of Schizophrenia, showing poor response to antipsychotic treatment, therefore non-pharmacological rehabilitative approaches to such a symptom domain need to be identified. However, since not all patients with Schizophrenia exhibit the same cognitive impairment profile, individualized rehabilitative approaches should be set up. Objectives: We explored the last five-year literature addressing the issue of cognitive dysfunction response to rehabilitative methodologies in Schizophrenia to identify possible predictors of response and individualized strategies to treat such a dysfunction. Conclusion: A total of 76 studies were reviewed. Possible predictors of cognitive rehabilitation outcome were identified among patient-specific and approachspecific variables and a general overview of rehabilitative strategies used in the last five years has been depicted. Studies suggest the existence of multifaced and multi-domain variables that could significantly predict pro-cognitive effects of cognitive rehabilitation, which could also be useful for identifying individual-specific rehabilitation trajectories over time. An individualized rehabilitative approach to cognitive impairment in Schizophrenia is possible if taking into account both patient and approach specific predictors of outcomes