29 research outputs found
The association between subjective anti-doping knowledge and objective knowledge among Japanese university athletes: a cross-sectional study
IntroductionThis study aimed to assess the association between subjective anti-doping knowledge (subjective ADK) and objective anti-doping knowledge (objective ADK) among Japanese university athletes, framed within the context of the Theory of Planned Behavior (TPB).MethodsEligible participants were 486 university athletes [320 men (65.8%), 166 women; mean age of 18.9 ± 1.0 years]. The participants categorized themselves in terms of the quality of their anti-doping knowledge. This assessment resulted in an independent variable coded as “(1) substantial lack of adequate knowledge,” “(2) some lack of adequate knowledge,” “(3) fair amount of knowledge” or “(4) good amount of knowledge.” Objective ADK was assessed using the Athlete Learning Program about Health and Anti-Doping (ALPHA) test, a set of questions derived from the ALPHA—a former World Anti-Doping Agency e-learning program. The test comprises 12 questions (four choices each; passing index: ≧10 points or 80% correct answer rate). ANCOVA was conducted using subjective ADK as an independent variable and ALPHA scores as a dependent variable, adjusting for confounding factors (anti-doping experience).ResultsThe ALPHA corrected answer rate across subjective ADK levels for the group were 73.10% for “(1) substantial lack of adequate knowledge,” 71.97% for “(2) some lack of adequate knowledge,” 75.18% for “(3) fair amount of knowledge” and 72.86% for “(4) good amount of knowledge.” Comparison between different levels of subjective ADK revealed no significant differences in ALPHA score considering the main effects or any of their interactions.DiscussionThe present results revealed that Japanese university athletes’ subjective ADK did not match their objective ADK. In the context of the TPB, there may be limitations in the perceived behavioral control in anti-doping knowledge. Even if athletes view doping as a wrongful act and have formed attitudes and subjective norms to comply with the rules, the results suggest that errors may occur in the composition of behavioral intentions due to a lack of knowledge. This could lead to the possibility of facing the risk of unintentional anti-doping rule violations. It highlights the need for targeted educational interventions to align subjective ADK of athletes with their objective ADK
SP-A Suppresses Lung Cancer Progression
Excel Spread Sheet of Sycan River, site SY-5, water surface elevation and a bed profile comparison from the dates 4/12/2004, 5/3/2005, 6/25/2004, and 05/13/2004
自由エネルギー表現内での静電的溶媒効果の理論的研究と溶媒反応への適用
京都大学0048新制・課程博士博士(理学)甲第15633号理博第3579号新制||理||1522(附属図書館)28170京都大学大学院理学研究科化学専攻(主査)准教授 林 重彦, 教授 谷村 吉隆, 教授 松本 吉泰学位規則第4条第1項該当Doctor of ScienceKyoto UniversityDA
Evaluation Procedure of Electrostatic Potential in 3D-RISM-SCF Method and Its Application to Hydrolyses of Cis- and Transplatin Complexes
In the three-dimensional reference interaction site model
self-consistent
field (3D-RISM-SCF) method, a switching function was introduced to
evaluate the electrostatic potential (ESP) around the solute to smoothly
connect the ESP directly calculated with the solute electronic wave
function and that approximately calculated with solute point charges.
Hydrolyses of cis- and transplatins, <i>cis</i>- and <i>trans</i>-PtCl<sub>2</sub>(NH<sub>3</sub>)<sub>2</sub>, were
investigated with this method. Solute geometries were optimized at
the DFT level with the M06-2X functional, and free energy changes
were calculated at the CCSD(T) level. In the first hydrolysis, the
calculated activation free energy is 20.8 kcal/mol for cisplatin and
20.3 kcal/mol for transplatin, which agrees with the experimental
and recently reported theoretical results. A Cl anion, which is formed
by the first hydrolysis, somehow favorably exists in the first solvation
shell as a counteranion. The second hydrolysis occurs with a similar
activation free energy (20.9 kcal/mol) for cisplatin but a somewhat
larger energy (23.2 kcal/mol) for transplatin to afford <i>cis</i>- and <i>trans</i>-diaqua complexes. The Cl counteranion
in the first solvation shell little influences the activation free
energy but somewhat decreases the endothermicity in both cis- and
transplatins. The present 3D-RISM-SCF method clearly displays the
microscopic solvation structure and its changes in the hydrolysis,
which are discussed in detail
3D-RISM-MP2 Approach to Hydration Structure of Pt(II) and Pd(II) Complexes: Unusual H‑Ahead Mode vs Usual O‑Ahead One
Solvation of transition metal complexes
with water has been one
of the fundamental topics in physical and coordination chemistry.
In particular, Pt(II) complexes have recently attracted considerable
interest for their relation to anticancer activity in cisplatin and
its analogues, yet the interaction of the water molecule and the metal
center has been obscured. The challenge from a theoretical perspective
remains that both the microscopic solvation effect and the dynamical
electron correlation (DEC) effect have to be treated simultaneously
in a reasonable manner. In this work we derive the analytical gradient
for the three-dimensional reference interaction site model Møller–Plesset
second order (3D-RISM-MP2) free energy. On the basis of the three-regions
3D-RISM self-consistent field (SCF) method recently proposed by us,
we apply a new layer of the Z-vector method to the CP-RISM equation
as well as point-charge approximation to the derivatives with respect
to the density matrix elements in the RISM-CPHF equation to remarkably
reduce the computational cost. This method is applied to study the
interaction of H<sub>2</sub>O with the d<sup>8</sup> square planar
transition metal complexes in aqueous solution, trans-[Pt<sup>II</sup>Cl<sub>2</sub>(NH<sub>3</sub>)(glycine)] (<b>1a</b>), [Pt<sup>II</sup>(NH<sub>3</sub>)<sub>4</sub>]<sup>2+</sup> (<b>1b</b>), [Pt<sup>II</sup>(CN)<sub>4</sub>]<sup>2–</sup> (<b>1c</b>), and their Pd(II) analogues <b>2a</b>, <b>2b</b>, and <b>2c</b>, respectively, to elucidate whether the usual H<sub>2</sub>O interaction through O atom (O-ahead mode) or unusual one through
H atom (H-ahead mode) is stable in these complexes. We find that the
interaction energy of the coordinating water and the transition metal
complex changes little when switching from gas to aqueous phase, but
the solvation free energy differs remarkably between the two interaction
modes, thereby affecting the relative stability of the H-ahead and
O-ahead modes. Particularly, in contrast to the expectation that the
O-ahead mode is preferred due to the presence of positive charges
in <b>1b</b>, the H-ahead mode is also found to be more stable.
The O-ahead mode is found to be more stable than the H-ahead one only
in <b>2b</b>. The energy decomposition analysis (EDA) at the
3D-RISM-MP2 level revealed that the O-ahead mode is stabilized by
the electrostatic (ES) interaction, whereas the H-ahead one is mainly
stabilized by the DEC effect. The ES interaction is also responsible
for the difference between the Pd(II) and Pt(II) complexes; because
the electrostatic potential is more negative along the <i>z</i>-axis in the Pt(II) complex than in the Pd(II) one, the O-ahead mode
prefers the Pd(II) complexes, whereas the H-ahead becomes predominant
in the Pt(II) complexes
Like-Charge Attraction of Molecular Cations in Water: Subtle Balance between Interionic Interactions and Ionic Solvation Effect
Despite strong electrostatic repulsion,
like-charged ions in aqueous
solution can effectively attract each other via ion–water interactions.
In this paper we investigate such an effective interaction of like-charged
ions in water by using the 3D-RISM-SCF method (i.e., electronic structure
theory combined with three-dimensional integral equation theory for
molecular solvents). Free energy profiles are calculated at the CCSD(T)
level for a series of molecular ions including guanidinium (Gdm<sup>+</sup>), alkyl-substituted ammonium, and aromatic amine cations.
Polarizable continuum model (PCM) and mean-field QM/MM free energy
calculations are also performed for comparison. The results show that
the stability of like-charged ion pairs in aqueous solution is determined
by a very subtle balance between interionic interactions (including
dispersion and π-stacking interactions) and ionic solvation/hydrophobic
effects and that the Gdm<sup>+</sup> ion has a rather favorable character
for like-charge association among all the cations studied. Furthermore,
we investigate the like-charge pairing in Arg-Ala-Arg and Lys-Ala-Lys
tripeptides in water and show that the Arg-Arg pair has a contact
free-energy minimum of about −6 kcal/mol. This result indicates
that arginine pairing observed on protein surfaces and interfaces
is stabilized considerably by solvation effects