Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge.

Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism

Real space mapping of topological invariants using artificial neural networks

Topological invariants allow to characterize Hamiltonians, predicting the existence of topologically protected in-gap modes. Those invariants can be computed by tracing the evolution of the occupied wavefunctions under twisted boundary conditions. However, those procedures do not allow to calculate a topological invariant by evaluating the system locally, and thus require information about the wavefunctions in the whole system. Here we show that artificial neural networks can be trained to identify the topological order by evaluating a local projection of the density matrix. We demonstrate this for two different models, a 1-D topological superconductor and a 2-D quantum anomalous Hall state, both with spatially modulated parameters. Our neural network correctly identifies the different topological domains in real space, predicting the location of in-gap states. By combining a neural network with a calculation of the electronic states that uses the Kernel Polynomial Method, we show that the local evaluation of the invariant can be carried out by evaluating a local quantity, in particular for systems without translational symmetry consisting of tens of thousands of atoms. Our results show that supervised learning is an efficient methodology to characterize the local topology of a system.Comment: 9 pages, 6 figure

Plasmon polaritons in photonic superlattices containing a left-handed material

We analyze one-dimensional photonic superlattices which alternate layers of air and a left-handed material. We assume Drude-type dispersive responses for the dielectric permittivity and magnetic permeability of the left-handed material. Maxwell's equations and the transfer-matrix technique are used to derive the dispersion relation for the propagation of obliquely incident optical fields. The photonic dispersion indicates that the growth-direction component of the electric (or magnetic) field leads to the propagation of electric (or magnetic) plasmon polaritons, for either TE or TM configurations. Furthermore, we show that if the plasma frequency is chosen within the photonic $=0$ zeroth-order bandgap, the coupling of light with plasmons weakens considerably. As light propagation is forbidden in that particular frequency region, the plasmon-polariton mode reduces to a pure plasmon mode.Comment: 4 pages, 4 figure

Response Of The Arterial Blood Pressure Of Quadriplegic Patients To Treadmill Gait Training.

Blood pressure pattern was analyzed in 12 complete quadriplegics with chronic lesions after three months of treadmill gait training. Before training, blood pressure values were obtained at rest, during treadmill walking and during the recovery phase. Gait training was performed for 20 min twice a week for three months. Treadmill gait was achieved using neuromuscular electrical stimulation, assisted by partial body weight relief (30-50%). After training, blood pressure was evaluated at rest, during gait and during recovery phase. Before and after training, mean systolic blood pressures and heart rates increased significantly during gait compared to rest (94.16 +/- 5.15 to 105 +/- 5.22 mmHg and 74.27 +/- 10.09 to 106.23 +/- 17.31 bpm, respectively), and blood pressure decreased significantly in the recovery phase (86.66 +/- 9.84 and 57.5 +/- 8.66 mmHg, respectively). After three months of training, systolic blood pressure became higher at rest (94.16 +/- 5.15 mmHg before training and 100 +/- 8.52 mmHg after training; P < 0.05) and during gait exercise (105 +/- 5.22 mmHg before and 110 +/- 7.38 mmHg after training; P < 0.05) when compared to the initial values, with no changes in heart rate. No changes occurred in blood pressure during the recovery phase, with the lower values being maintained. A drop in systolic pressure from 105 +/- 5.22 to 86.66 +/- 9.84 mmHg before training and from 110 +/- 7.38 to 90 +/- 7.38 mmHg after training was noticed immediately after exercise, thus resulting in hypotensive symptoms when chronic quadriplegics reach the sitting position from the upright position.381367-7

Regulatory focus and sexual health: Motives for security and pleasure in sexuality are associated with distinct protective behaviors

We examined if motives for security (i.e., prevention focus) or pleasure (i.e., promotion focus) were uniquely associated with intentions to get tested for STIs and behavioral control over condom use, over and above variables already identified in theoretical models. We conducted an online survey with Portuguese adults (N = 836; Mage = 22.27, SD = 5.14). Overall, 99.4% of the participants knew at least one of eight STIs, but only 25.2% got tested in the last six months. Participants more focused on prevention had condomless sex less frequently, whereas participants more focused on promotion knew more STIs and got tested for more STIs. Furthermore, participants had stronger intentions to get tested for STIs if they got tested for more STIs in the past, were more concerned about STIs, perceived greater susceptibility to STI acquisition, and were more focused on promotion (but not prevention). Participants had greater behavioral control over condom use if they had condomless sex less often and were more focused on prevention (but not promotion). These findings suggest that promotion-focused people are more likely to consider the consequences of having condomless sex. In contrast, prevention-focused people are more likely to take control of their sexual health.info:eu-repo/semantics/acceptedVersio