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1.
Chirality ; 35(5): 298-310, 2023 05.
Artigo em Inglês | MEDLINE | ID: mdl-36775278

RESUMO

In this study, we exploit a recently developed fragment diabatization-based excitonic model, FrDEx, to simulate the electronic circular dichroism (ECD) spectra of three guanine-rich DNA sequences arranged in guanine quadruple helices with different topologies: thrombin binding aptamer (antiparallel), c-Myc promoter (parallel), and human telomeric sequence (3+1 hybrid). Starting from time-dependent density functional theory (TD-DFT) calculations with the M052X functional, we apply our protocol to parameterize the FrDEX Hamiltonian, which accounts for electron density overlap and includes both the coupling with charge transfer transitions and the effect of the surrounding bases on the local excitation of each chromophore. The TD-DFT/M052X spectral shapes are in good agreement with the experimental ones, the main source of discrepancy being related to the intrinsic error on the computed transition energies of guanine monomer. FrDEx spectra are fairly close to the reference TD-DFT ones, allowing a significant advance with respect to a more standard excitonic Hamiltonian. We also show that the ECD spectra are sensitive to the inclusion of the inner K + cation in the calculation.


Assuntos
DNA , Teoria Quântica , Humanos , Dicroísmo Circular , Estereoisomerismo , Eletrônica , Guanina
2.
Chemistry ; 28(57): e202203016, 2022 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-36202627

RESUMO

Invited for the cover of this issue is the group of G. A. Worth, F. Santoro and R. Improta at UCL, ICOOM-CNR and IBB-CNR. The image depicts charge transfer from guanine to cytosine in solvent after the absorption of light. Read the full text of the article at 10.1002/chem.202201731.


Assuntos
Citosina , Guanina , Clorofórmio , Solventes
3.
Chemistry ; 28(57): e202201731, 2022 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-35950519

RESUMO

We study the ultrafast photoactivated dynamics of the hydrogen bonded dimer Guanine-Cytosine in chloroform solution, focusing on the population of the Guanine→Cytosine charge transfer state (GC-CT), an important elementary process for the photophysics and photochemistry of nucleic acids. We integrate a quantum dynamics propagation scheme, based on a linear vibronic model parameterized through time dependent density functional theory calculations, with four different solvation models, either implicit or explicit. On average, after 50 fs, 30∼40 % of the bright excited state population has been transferred to GC-CT. This process is thus fast and effective, especially when transferring from the Guanine bright excited states, in line with the available experimental studies. Independent of the adopted solvation model, the population of GC-CT is however disfavoured in solution with respect to the gas phase. We show that dynamical solvation effects are responsible for this puzzling result and assess the different chemical-physical effects modulating the population of CT states on the ultrafast time-scale. We also propose some simple analyses to predict how solvent can affect the population transfer between bright and CT states, showing that the effect of the solute/solvent electrostatic interactions on the energy of the CT state can provide a rather reliable indication of its possible population.


Assuntos
Citosina , Ácidos Nucleicos , Clorofórmio , Guanina , Hidrogênio , Teoria Quântica , Solventes
4.
Phys Chem Chem Phys ; 23(14): 8181-8199, 2021 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-33875988

RESUMO

We concisely review the main methodological approaches to model nonadiabatic dynamics in isotropic solutions and their applications. Three general classes of models are identified as the most used to include solvent effects in the simulations. The first model describes the solvent as a set of harmonic collective modes coupled to the solute degrees of freedom, and the second as a continuum, while the third explicitly includes solvent molecules in the calculations. The issues related to the use of these models in semiclassical and quantum dynamical simulations are discussed, as well as the main limitations and perspectives of each approach.

5.
J Phys Chem A ; 125(40): 8912-8924, 2021 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-34609880

RESUMO

In this contribution we present a quantum dynamical study of the photoexcited hydrogen bonded base pair adenine-thymine (AT) in a Watson-Crick arrangement. To that end, we parametrize Linear Vibronic Coupling (LVC) models with Time-Dependent Density Functional Theory (TD-DFT) calculations, exploiting a fragment diabatization scheme (FrD) we have developed to define diabatic states on the basis of individual chromophores in a multichromophoric system. Wavepacket propagations were run with the multilayer extension of the Multiconfiguration Time-Dependent Hartree method. We considered excitations to the three lowest bright states, a ππ* state of thymine and two ππ* states (La and Lb) of adenine, and we found that on the 100 fs time scale the main decay pathways involve intramonomer population transfers toward nπ* states of the same nucleobase. In AT this transfer is less effective than in the isolated nucleobases, because hydrogen bonding destabilizes the nπ* states. The population transfer to the A → T charge transfer state is negligible, making the ultrafast (femtosecond) decay through the proton coupled electron transfer mechanism unlikely, in line with experimental results in apolar solvents. The excitation energy transfer is also very small. We carefully compare the predictions of LVC Hamiltonians obtained with different sets of diabatic states, defined so to match either local states of the two separated monomers or the base pair adiabatic states in the Franck-Condon region. To that end we also extend the flexibility of the FrD-LVC approach, introducing a new strategy to define fragments diabatic states that account for the effect of the rest of the multichromohoric system through a Molecular Mechanics potential.

6.
Molecules ; 26(6)2021 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-33804640

RESUMO

We have recently proposed a protocol for Quantum Dynamics (QD) calculations, which is based on a parameterisation of Linear Vibronic Coupling (LVC) Hamiltonians with Time Dependent (TD) Density Functional Theory (TD-DFT), and exploits the latest developments in multiconfigurational TD-Hartree methods for an effective wave packet propagation. In this contribution we explore the potentialities of this approach to compute nonadiabatic vibronic spectra and ultrafast dynamics, by applying it to the five nucleobases present in DNA and RNA. For all of them we computed the absorption spectra and the dynamics of ultrafast internal conversion (100 fs timescale), fully coupling the first 2-3 bright states and all the close by dark states, for a total of 6-9 states, and including all the normal coordinates. We adopted two different functionals, CAM-B3LYP and PBE0, and tested the effect of the basis set. Computed spectra are in good agreement with the available experimental data, remarkably improving over pure electronic computations, but also with respect to vibronic spectra obtained neglecting inter-state couplings. Our QD simulations indicate an effective population transfer from the lowest energy bright excited states to the close-lying dark excited states for uracil, thymine and adenine. Dynamics from higher-energy states show an ultrafast depopulation toward the more stable ones. The proposed protocol is sufficiently general and automatic to promise to become useful for widespread applications.


Assuntos
DNA/química , Modelos Químicos , RNA/química , Adenina/química , Citosina/química , Timina/química , Uracila/química
7.
Molecules ; 26(16)2021 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-34443377

RESUMO

We here investigate the Electronic Circular Dichroism (ECD) Spectra of two representative Guanine-rich sequences folded in a Quadruple helix (GQ), by using a recently developed fragment diabatisation based excitonic model (FrDEx). FrDEx can include charge transfer (CT) excited states and consider the effect of the surrounding monomers on the local excitations (LEs). When applied to different structures generated by molecular dynamics simulations on a fragment of the human telomeric sequence (Tel21/22), FrDEx provides spectra fully consistent with the experimental one and in good agreement with that provided by quantum mechanical (QM) method used for its parametrization, i.e., TD-M05-2X. We show that the ECD spectrum is moderately sensitive to the conformation adopted by the bases of the loops and more significantly to the thermal fluctuations of the Guanine tetrads. In particular, we show how changes in the overlap of the tetrads modulate the intensity of the ECD signal. We illustrate how this correlates with changes in the character of the excitonic states at the bottom of the La and Lb bands, with larger LE and CT involvement of bases that are more closely stacked. As an additional test, we utilised FrDEx to compute the ECD spectrum of the monomeric and dimeric forms of a GQ forming sequence T30695 (5'TGGGTGGGTGGGTGGG3'), i.e., a system containing up to 24 Guanine bases, and demonstrated the satisfactory reproduction of the experimental and QM reference results. This study provides new insights on the effects modulating the ECD spectra of GQs and, more generally, further validates FrDEx as an effective tool to predict and assign the spectra of closely stacked multichromophore systems.


Assuntos
Dicroísmo Circular , DNA/química , Elétrons , Simulação de Dinâmica Molecular , Conformação de Ácido Nucleico , Dimerização , Espectroscopia de Ressonância Magnética , Temperatura
8.
Phys Chem Chem Phys ; 22(10): 5509-5522, 2020 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-32104818

RESUMO

We compute at the anharmonic level the vibrational spectra of the Watson-Crick dimer formed by guanosine (G) and cytidine (C) in chloroform, together with those of G, C and the most populated GG dimer. The spectra for deuterated and partially deuterated GC are also computed. We use DFT calculations, with B3LYP and CAM-B3LYP as reference functionals. Solvent effects from chloroform are included via the Polarizable Continuum Model (PCM), and by performing tests on models including up two chloroform molecules. Both B3LYP and CAM-B3LYP calculations reproduce the shape of the experimental spectra well in the fingerprint region (1500-1700 cm-1) and in the N-H stretching region (2800-3600 cm-1), with B3LYP providing better quantitative agreement with experiments. According to our calculations, the N-H amido streching mode of G falls at ∼2900 cm-1, while the N-H amino of G and C falls at ∼3100 cm-1 when hydrogen-bonded, or ∼3500 cm-1 when free. Overtone and combination bands strongly contribute to the absorption band at ∼3300 cm-1. Inclusion of bulk solvent effects significantly increases the accuracy of the computed spectra, while solute-solvent interactions have a smaller, though still noticeable, effect. Some key aspects of the anharmonic treatment of strongly vibrationally coupled supermolecular systems and the related methodological issues are also discussed.


Assuntos
Clorofórmio/química , Citosina/química , Guanina/química , Vibração , Química Computacional
9.
Memory ; 28(5): 589-597, 2020 05.
Artigo em Inglês | MEDLINE | ID: mdl-32378455

RESUMO

Cognitive scientists have firmly established that memory is vulnerable to decay and distortion. Yet laypeople - who may be required to evaluate memory evidence as jurors - have shown less awareness of memory fallibility. Although we might expect laypeople's knowledge of memory to have improved over time, research has yet to explore this issue while accounting for possible age-related changes. We administered a modified version of the Beliefs about Memory Survey (BAMS) to a community sample, investigating patterns of beliefs relating to memory permanence, repression of traumatic memories, and memory reconstruction. Older participants were more likely than younger participants to believe that traumatic memories can be repressed, while younger participants were more likely than their older counterparts to believe that memory is permanent, but also that memory is malleable. We assessed whether these beliefs were stable over time, by comparing our data to a sample of data collected 25 years earlier. Although contemporary beliefs about the repression of traumatic memories and memory reconstruction were more aligned with expert opinion than those of 25 years ago, beliefs about memory permanence were not. These findings highlight the need for continued education about memory and its shortcomings. We discuss ways of improving decisions about memory evidence.


Assuntos
Prova Pericial , Memória/fisiologia , Repressão Psicológica , Adulto , Fatores Etários , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Fatores Sexuais , Inquéritos e Questionários
10.
Phys Chem Chem Phys ; 21(19): 9987-9995, 2019 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-31041956

RESUMO

We present results obtained using the ab initio multiple cloning (AIMC) method to simulate fully quantum dynamics for imidazole and its structural isomer pyrazole along with their selectively deuterated species. We simulate the ultrafast dissociation of the N-H/D bond for these molecules along the repulsive 1πσ* state which agrees well with previous experimental results. Our results give evidence for a two-stage dissociation of the N-H/D bond on the sub-50 fs regime for imidazole, pyrazole and their selectively deuterated species, and give evidence for the importance of the repulsive 1πσ* state along the N-H/D bond coordinate for the relaxation of both imidazole and pyrazole. The ability of these calculations to reproduce experimental results lends confidence that larger complex systems could be explored with predictive capabilities with the AIMC method. These results also confirm the ability of the AIMC method to add detailed insights into which experiments are blind.

11.
Phys Chem Chem Phys ; 21(7): 3832-3841, 2019 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-30698166

RESUMO

The ultrafast photodissociation dynamics of 2-ethylpyrrole (2-EP) is simulated in a fully quantum manner on the S1 and S2 πσ* states by the ab initio multiple cloning (AIMC) method. AIMC treats electrons with accurate electronic structure methods "on the fly", and nuclear dynamics with wavefunction propagation via a basis set of Ehrenfest trajectory guided Gaussian wavepackets. Total kinetic energy release (TKER) spectra are produced, as well as velocity map images and N-H dissociation times. These are compared to results from time-resolved velocity map imaging studies, and the AIMC method is able to provide quantitative reproduction of experimental data, including dissociation times of 50-80 fs. Novel insight into the dissociation mechanism is then obtained, with the experimentally obtained time constant shown to be composed of two components. Firstly, there is a contribution in <50 fs from 2-EP molecules that have sufficient energy in the N-H stretch coordinate to dissociate almost immediately over the barrier, and this is followed by a second slower contribution from 2-EP molecules that must sample the potential energy surface before finding a way around the barrier to dissociate. This two component mechanism is not observed experimentally due to the temporal widths of the laser pulses obscuring the dynamics in the <50 fs window, and is shown for the first time via theory. Calculations are also performed on selectively deuterated 2-EP, demonstrating that AIMC is able to produce a kinetic isotope effect for the dissociation time constant, and correctly predict a shift to lower energy in the TKER spectrum. The S2 πσ* state is also shown to be unstable with respect to the S1 πσ* state, with the N-H dissociation proceeding along S1 when initially excited to S2. This work demonstrates that the combination of state of the art theory and experiments can provide unprecedented novel insight into the N-H dissociation mechanism, with the tantalising prospect of providing insight into more general heteroatom hydride bond dissociation.

12.
J Chem Phys ; 144(2): 024111, 2016 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-26772558

RESUMO

In this paper, a two-layer scheme is outlined for the coupled coherent states (CCS) method, dubbed two-layer CCS (2L-CCS). The theoretical framework is motivated by that of the multiconfigurational Ehrenfest method, where different dynamical descriptions are used for different subsystems of a quantum mechanical system. This leads to a flexible representation of the wavefunction, making the method particularly suited to the study of composite systems. It was tested on a 20-dimensional asymmetric system-bath tunnelling problem, with results compared to a benchmark calculation, as well as existing CCS, matching-pursuit/split-operator Fourier transform, and configuration interaction expansion methods. The two-layer method was found to lead to improved short and long term propagation over standard CCS, alongside improved numerical efficiency and parallel scalability. These promising results provide impetus for future development of the method for on-the-fly direct dynamics calculations.

13.
Adv Health Sci Educ Theory Pract ; 20(1): 219-28, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-24988998

RESUMO

Non-local ethnicity or nationality and lower English proficiency have been linked with poor performance in health professional education. This study sought to compare the relative contributions of ethnicity and English proficiency, and to do so in a context where students had not been selected via interviews or some other proxy for language proficiency. Ethnicity, citizenship, and demographic data, as well as academic performance and progress were obtained for three successive cohorts (entering in 2007, 2008 and 2009) into a three-year pharmacy programme, following a common first-year. Complete data was available for all 297 students entering via this path. By the end of the programme, controlling for grades at entry, students from some non-local ethnic backgrounds (p < .001) underperformed local students, as did males (p < .001) and those who had been identified as having low English proficiency in year 1 (p < .01). Males (p < .01) and one non-local ethnic group (p < .01) were also more likely to have to repeat a year of study. Ethnicity was a stronger predictor than English proficiency or acculturation, but English proficiency was still independently and additively predictive. This suggests that targeted support strategies for students with lower English language proficiency are still important, but that cultural differences should not be underestimated.


Assuntos
Logro , Educação em Farmácia , Avaliação Educacional , Etnicidade , Idioma , Feminino , Humanos , Masculino , Nova Zelândia , Adulto Jovem
14.
Health Psychol Behav Med ; 12(1): 2351939, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38817594

RESUMO

Open Science practices are integral to increasing transparency, reproducibility, and accessibility of research in health psychology and behavioral medicine. Drives to facilitate Open Science practices are becoming increasingly evident in journal editorial policies, including the establishment of new paper formats such as Registered Reports and Data Notes. This paper provides: (i) an overview of the current state of Open Science policies within health psychology and behavioral medicine, (ii) a call for submissions to an Article Collection of Registered Reports and Data Notes as new paper formats within the journal of Health Psychology & Behavioral Medicine, (iii) an overview of Registered Reports and Data Notes, and (iv) practical considerations for authors and reviewers of Registered Reports and Data Notes.

15.
BMC Neurosci ; 14: 96, 2013 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-24011083

RESUMO

BACKGROUND: Myelinated axons are organized into distinct subcellular and molecular regions. Without proper organization, electrical nerve conduction is delayed, resulting in detrimental physiological outcomes. One such region is the paranode where axo-glial septate junctions act as a molecular fence to separate the sodium (Na+) channel-enriched node from the potassium (K+) channel-enriched juxtaparanode. A significant lack of knowledge remains as to cytoskeletal proteins which stabilize paranodal domains and underlying cytoskeleton. Whirlin (Whrn) is a PDZ domain-containing cytoskeletal scaffold whose absence in humans results in Usher Syndromes or variable deafness-blindness syndromes. Mutant Whirlin (Whrn) mouse model studies have linked such behavioral deficits to improper localization of critical transmembrane protein complexes in the ear and eye. Until now, no reports exist about the function of Whrn in myelinated axons. RESULTS: RT-PCR and immunoblot analyses revealed expression of Whrn mRNA and Whrn full-length protein, respectively, in several stages of central and peripheral nervous system development. Comparing wild-type mice to Whrn knockout (Whrn-/-) mice, we observed no significant differences in the expression of standard axonal domain markers by immunoblot analysis but observed and quantified a novel paranodal compaction phenotype in 4 to 8 week-old Whrn-/- nerves. The paranodal compaction phenotype and associated cytoskeletal disruption was observed in Whrn-/- mutant sciatic nerves and spinal cord fibers from early (2 week-old) to late (1 year-old) stages of development. Light and electron microscopic analyses of Whrn knockout mice reveal bead-like swellings in cerebellar Purkinje axons containing mitochondria and vesicles by both. These data suggest that Whrn plays a role in proper cytoskeletal organization in myelinated axons. CONCLUSIONS: Domain organization in myelinated axons remains a complex developmental process. Here we demonstrate that loss of Whrn disrupts proper axonal domain organization. Whrn likely contributes to the stabilization of paranodal myelin loops and axonal cytoskeleton through yet unconfirmed cytoskeletal proteins. Paranodal abnormalities are consistently observed throughout development (2 wk-1 yr) and similar between central and peripheral nervous systems. In conclusion, our observations suggest that Whrn is not required for the organization of axonal domains, but once organized, Whrn acts as a cytoskeletal linker to ensure proper paranodal compaction and stabilization of the axonal cytoskeleton in myelinated axons.


Assuntos
Citoesqueleto/ultraestrutura , Proteínas de Membrana/metabolismo , Fibras Nervosas Mielinizadas/ultraestrutura , Animais , Axônios/metabolismo , Axônios/ultraestrutura , Citoesqueleto/metabolismo , Eletrofisiologia , Immunoblotting , Imuno-Histoquímica , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Knockout , Microscopia Eletrônica de Transmissão , Fibras Nervosas Mielinizadas/metabolismo , Nós Neurofibrosos/metabolismo , Nós Neurofibrosos/ultraestrutura , Reação em Cadeia da Polimerase Via Transcriptase Reversa
16.
Res Social Adm Pharm ; 19(4): 634-642, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36702707

RESUMO

BACKGROUND: Schools and faculties of pharmacy are responsible for selecting students to admit into the profession. Despite many similarities, admission processes, pharmacists' training, and scope of practice are different across jurisdictions. Students that are selected for admission may then differ in a number of ways, including by personality traits and other individual difference measures. OBJECTIVE: To compare the trait characteristics between students entering a New Zealand (NZ-University of Otago) and Canadian ((University of Waterloo) pharmacy programme and to compare their professional goals and role perceptions. METHODS: Incoming first year students at each university were invited to take an online questionnaire that included personality characteristics and potential predictors of involvement in pharmacists' roles: (1) the Big Five Inventory (openness, conscientiousness, extraversion, agreeableness, neuroticism); (2) the Achievement Goals Questionnaire-Revised; (3) the Rational Experiential Inventory; and (4) Counsellor Role Orientation. Statistical tests were conducted to determine if there were differences between entry level pharmacy students from NZ and Canada. RESULTS: 184 students (97/150 Otago, 87/118 Waterloo) completed the survey. On average, Waterloo students scored higher on agreeableness (M = 80 vs. 76, p = 0.06), conscientiousness (M = 70 vs. 68, p = 0.30), mastery-approach (M = 93 vs.90, p = 0.06), and faith-in-intuition (M = 67 vs. 61, p = 0.03) compared to Otago pharmacy students who were higher for openness M = 70 vs. 66, p = 0.09). An item measuring reliance on physicians for medicine advice was endorsed more by Otago pharmacy students (M = 35 vs. M = 15, p < 0.001). Items on time pressure (e.g., "It takes too much time to for a pharmacist to talk with a patient about the medication they receive") were higher for Otago students (M = 41 vs. M = 38, p = 0.26). Higher scores for pharmacist restriction ("There should be legal restrictions on what pharmacists can tell patients") were also seen among Otago students (M = 26 vs. M = 12, p < 0.001). There were important differences between entry level pharmacy students and practicing pharmacists in both jurisdictions. DISCUSSION: While entry-level pharmacy students had similar personality profiles, differences were observed in role expectations and in experiential learning orientation. This highlights differing societal views on the role of pharmacists in each respective country. Pharmacy schools should study their student bodies when designing their curricula and electives, helping ensure graduates feel like they have the training to do what they need to do. Future work will determine if these personality and learning goals influence students' preparation for practice.


Assuntos
Educação em Farmácia , Assistência Farmacêutica , Estudantes de Farmácia , Humanos , Objetivos , Canadá , Personalidade , Inquéritos e Questionários , Farmacêuticos , Papel Profissional
17.
J Phys Chem B ; 126(50): 10608-10621, 2022 12 22.
Artigo em Inglês | MEDLINE | ID: mdl-36508709

RESUMO

Here we refine and assess two computational procedures aimed to include the effect of thermal fluctuations on the electronic spectra and the ultrafast excited state dynamics of multichromophore systems, focusing on DNA duplexes. Our approach is based on a fragment diabatization procedure that, from a given Quantum Mechanical (QM) reference method, can provide the parameters (energy and coupling) of the reference diabatic states on the basis of the isolated fragments, either for a purely electronic excitonic Hamiltonian (FrDEx) or a linear vibronic coupling Hamiltonian (FrD-LVC). After having defined the most cost-effective procedure for DNA duplexes on two smaller fragments, FrDEx is used to simulate the absorption and Electronic Circular Dichroism (ECD) spectra of (GC)5 sequences, including the coupling with the Charge Transfer (CT) states, on a number of structures extracted from classical Molecular Dynamics (MD) simulations. The computed spectra are close to the reference TD-DFT calculations and fully consistent with the experimental ones. We then couple MD simulations and FrD-LVC to simulate the interplay between local excitations and CT transitions, both intrastrand and interstrand, in GC and CG steps when included in a oligoGC or in oligoAT DNA sequence. We predict that for both sequences a substantial part of the photoexcited population on G and C decays, within 50-100 fs, to the corresponding intrastrand CT states. This transfer is more effective for GC steps that, on average, are more closely stacked than CG ones.


Assuntos
DNA , Teoria Quântica , DNA/química , Simulação de Dinâmica Molecular , Dicroísmo Circular , Teoria da Densidade Funcional
18.
Psychol Health ; : 1-25, 2022 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-36317294

RESUMO

OBJECTIVE: Research on Open Science practices in Health Psychology is lacking. This meta-research study aimed to identify research question priorities and obtain consensus on the Top 5 prioritised research questions for Open Science in Health Psychology. METHODS AND MEASURES: An international Delphi consensus study was conducted. Twenty-three experts in Open Science and Health Psychology within the European Health Psychology Society (EHPS) suggested research question priorities to create a 'long-list' of items (Phase 1). Forty-three EHPS members rated the importance of these items, ranked their top five and suggested their own additional items (Phase 2). Twenty-four EHPS members received feedback on Phase 2 responses and then re-rated and re-ranked their top five research questions (Phase 3). RESULTS: The top five ranked research question priorities were: 1. 'To what extent are Open Science behaviours currently practised in Health Psychology?', 2. 'How can we maximise the usefulness of Open Data and Open Code resources?', 3. 'How can Open Data be increased within Health Psychology?', 4. 'What interventions are effective for increasing the adoption of Open Science in Health Psychology?' and 5. 'How can we increase free Open Access publishing in Health Psychology?'. CONCLUSION: Funding and resources should prioritise the research questions identified here.

19.
J Chem Theory Comput ; 18(6): 3718-3736, 2022 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-35377648

RESUMO

In this contribution we present a mixed quantum-classical dynamical approach for the computation of vibronic absorption spectra of molecular aggregates and their nonadiabatic dynamics, taking into account the coupling between local excitations (LE) and charge-transfer (CT) states. The approach is based on an adiabatic (Ad) separation between the soft degrees of freedom (DoFs) of the system and the stiff vibrations, which are described by the quantum dynamics (QD) of wave packets (WPs) moving on the coupled potential energy surfaces (PESs) of the LE and CT states. These PESs are described with a linear vibronic coupling (LVC) Hamiltonian, parameterized by an overlap-based diabatization on the grounds of time-dependent density functional theory computations. The WPs time evolution is computed with the multiconfiguration time-dependent Hartree method, using effective modes defined through a hierarchical representation of the LVC Hamiltonian. The soft DoFs are sampled with classical molecular dynamics (MD), and the coupling between the slow and fast DoFs is included by recomputing the key parameters of the LVC Hamiltonians, specifically for each MD configuration. This method, named Ad-MD|gLVC, is applied to a perylene diimide (PDI) dimer in acetonitrile and water solutions, and it is shown to accurately reproduce the change in the vibronic features of the absorption spectrum upon aggregation. Moreover, the microscopic insight offered by the MD trajectories allows for a detailed understanding of the role played by the fluctuation of the aggregate structure on the shape of the vibronic spectrum and on the population of LE and CT states. The nonadiabatic QD predicts an extremely fast (∼50 fs) energy transfer between the two LEs. CT states have only a moderate effect on the absorption spectrum, despite the fact that after photoexcitation they are shown to acquire a fast and non-negligible population, highlighting their relevance in dictating the charge separation and transport in PDI-based optical devices.

20.
Health Psychol Behav Med ; 9(1): 436-455, 2021 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-34104569

RESUMO

Background: Dependent variables in health psychology are often counts, for example, of a behaviour or number of engagements with an intervention. These counts can be very strongly skewed, and/or contain large numbers of zeros as well as extreme outliers. For example, 'How many cigarettes do you smoke on an average day?' The modal answer may be zero but may range from 0 to 40+. The same can be true for minutes of moderate-to-vigorous physical activity. For some people, this may be near zero, but take on extreme values for someone training for a marathon. Typical analytical strategies for this data involve explicit (or implied) transformations (smoker v. non-smoker, log transformations). However, these data types are 'counts' (i.e. non-negative whole numbers) or quasi-counts (time is ratio but discrete minutes of activity could be analysed as a count), and can be modelled using count distributions - including the Poisson and negative binomial distribution (and their zero-inflated and hurdle extensions, which alloweven more zeros). Methods: In this tutorial paper I demonstrate (in R, Jamovi, and SPSS) the easy application of these models to health psychology data, and their advantages over alternative ways of analysing this type of data using two datasets - one highly dispersed dependent variable (number of views on YouTube, and another with a large number of zeros (number of days on which symptoms were reported over a month). Results: The negative binomial distribution had the best fit for the overdispersed number of views on YouTube. Negative binomial, and zero-inflated negative binomial were both good fits for the symptom data with over-abundant zeros. Conclusions: In both cases, count distributions provided not just a better fit but would lead to different conclusions compared to the poorly fitting traditional regression/linear models.

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