Adhesion of bis-salphen-based coordination polymers to graphene: insights from free energy perturbation study

Manipulation of nanoscale objects using molecular self-assembly is a potent tool to achieve large scale nanopatterning with small effort. Coordination polymers of bis-salphen compounds based on zinc have demonstrated their ability to align carbon nanotubes into micro-scale networks with an unusual “rings-and-rods” pattern. This paper investigates how the compounds interact with pristine and functionalized graphene using density functional theory calculations and molecular dynamic simulations. Using the free energy perturbation method we will show how the addition of phenyl side groups to the core compound and functionalization of graphene affect the stability, mobility and conformation adopted by a dimer of bis-(Zn)salphen compound adsorbed on graphene surface and what it can reveal about the arrangement of chains of bis-(Zn)salphen polymer around carbon nanotubes during the self-assembly of microscale networks.This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2020 and projects SATRAP (POCI-01-442 0145-FEDER-028108) and SATRAP-PLUS (EXPL/FIS-MAC/0947/2021)

Distinct frequencies balance segregation with interaction between different memory types within a prefrontal circuit

Once formed, the fate of memory is uncertain. Subsequent offline interactions between even different memory types (actions versus words) modify retention.1,2,3,4,5,6 These interactions may occur due to different oscillations functionally linking together different memory types within a circuit.7,8,9,10,11,12,13 With memory processing driving the circuit, it may become less susceptible to external influences.14 We tested this prediction by perturbing the human brain with single pulses of transcranial magnetic stimulation (TMS) and simultaneously measuring the brain activity changes with electroencephalography (EEG15,16,17). Stimulation was applied over brain areas that contribute to memory processing (dorsolateral prefrontal cortex, DLPFC; primary motor cortex, M1) at baseline and offline, after memory formation, when memory interactions are known to occur.1,4,6,10,18 The EEG response decreased offline (compared with baseline) within the alpha/beta frequency bands when stimulation was applied to the DLPFC, but not to M1. This decrease exclusively followed memory tasks that interact, revealing that it was due specifically to the interaction, not task performance. It remained even when the order of the memory tasks was changed and so was present, regardless of how the memory interaction was produced. Finally, the decrease within alpha power (but not beta) was correlated with impairment in motor memory, whereas the decrease in beta power (but not alpha) was correlated with impairment in word-list memory. Thus, different memory types are linked to different frequency bands within a DLPFC circuit, and the power of these bands shapes the balance between interaction and segregation between these memories

GAFF-IC: realistic viscosities for isocyanate molecules with a GAFF-based force field

Aliphatic diisocyanates and their derivatives are key liquid components in the industrial processing of polyurethane materials. In particular, for the synthesis of crosslinked polyurethane materials, the higher functionality molecules obtained by reacting three -or more- diisocyanates are of interest. However, despite their widespread application, the relation between molecular structure and macroscopic physical properties, in particular viscosity, is poorly understood in these systems. In this work, we introduce a new force field parameter set, GAFF-IC, based on the widely-used and versatile GAFF force field, meant for accurate predictions of physical properties of isocyanate-based molecular liquids. The new parameters allow to predict the vaporization enthalpies and densities of several isocyanate-based molecules, which are found in excellent agreement with the available experimental data. The effectiveness and transferability of the improved parameters is verified by calculating the viscosities of several isocyanates, isocyanate dimers (uretdiones) and isocyanate trimers (isocyanurates), resulting in accurate viscosity predictions in excellent agreement with experimental values.This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sk lodowska-Curie Grant Agreement no. 642890 (http://thelink-project.eu/) and it was partially supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013, and by the project ”Search-ON2: Revitalization of HPC infrastructure of Uminho” (NORTE-07-0162-FEDER-0000869), under the National Strategic Reference Framework, through the European Regional Development Fun

Ferroelectricity and negative piezoelectric coefficient in orthorhombic phase pure ZrO2 thin films

A new approach for epitaxial stabilisation of ferroelectric orthorhombic (o-) ZrO2 films with negative piezoelectric coefficient in ∼ 8nm thick films grown by ion-beam sputtering is demonstrated. Films on (011)-Nb:SrTiO3 gave the oriented o-phase, as confirmed by transmission electron microscopy and electron backscatter diffraction mapping, grazing incidence x-ray diffraction and Raman spectroscopy. Scanning probe microscopy techniques and macroscopic polarization-electric field hysteresis loops show ferroelectric behavior, with saturation polarization of ∼14.3 µC/cm2, remnant polarization of ∼9.3 µC/cm2 and coercive field ∼1.2 MV/cm. In contrast to the o-films grown on (011)-Nb:SrTiO3, films grown on (001)-Nb:SrTiO3 showed mixed monoclinic (m-) and o-phases causing an inferior remnant polarization of ∼4.8 µC/cm2, over 50% lower than the one observed for the film grown on (011)-Nb:SrTiO3. Density functional theory (DFT) calculations of the SrTiO3/ZrO2 interfaces support the experimental findings of a stable polar o-phase for growth on (011) Nb:SrTiO3, and they also explain the negative piezoelectric coefficient.This work was supported by: (i) the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding Contract UIDB/04650/2020 and (ii) Project NECL - NORTE-01-0145-FEDER-022096 and Project UID/NAN/50024/2019. This work has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 958174 (M-ERA-NET3/0003/2021 - NanOx4EStor). This work was also developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology/MCTES. It is also funded by national funds (OE), through FCT – Fundação para a Ciência e a Tecnologia, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19.The calculations were carried out at the OBLIVION Supercomputer (based at the High Performance Computing Center - University of Évora) funded by the ENGAGE SKA Research Infrastructure (reference POCI-01-0145-FEDER-022217 - COMPETE 2020 and the Foundation for Science and Technology, Portugal) and by the BigData@UE project (reference ALT20-03-0246-FEDER-000033 - FEDER and the Alentejo 2020 Regional Operational Program). Oblivion resources were accessed through the advanced computing projects CPCA/A2/5649/2020 and CPCA/A2/4628/2020, funded by FCT I.P. The authors gratefully acknowledge the HPC RIVR consortium (www.hpc-rivr.si) and EuroHPC JU (eurohpc-ju.europa.eu) for funding this research by providing computing resources of the HPC system Vega at the Institute of Information Science (www.izum.si)The calculations were carried out at the OBLIVION Supercomputer (based at the High Performance Computing Center - University of Évora) funded by the ENGAGE SKA Research Infrastructure (reference POCI-01-0145-FEDER-022217 - COMPETE 2020 and the Foundation for Science and Technology, Portugal) and by the BigData@UE project (reference ALT20-03-0246-FEDER-000033 - FEDER and the Alentejo 2020 Regional Operational Program). Oblivion resources were accessed through the advanced computing projects CPCA/A2/5649/2020 and CPCA/A2/4628/2020, funded by FCT I.P. The authors gratefully acknowledge the HPC RIVR consortium (www.hpc-rivr.si) and EuroHPC JU (eurohpc-ju.europa.eu) for funding this research by providing computing resources of the HPC system Vega at the Institute of Information Science (www.izum.si

Ferroelectric orthorhombic ZrO2 thin films achieved through nanosecond laser annealing

A new approach for the stabilization of the ferroelectric orthorhombic ZrO2 films is demonstrated through nanosecond laser annealing (NLA) of as-deposited Si/SiOx/W(14 nm)/ZrO2(8 nm)/W(22 nm), grown by ion beam sputtering at low temperatures. The NLA process optimization is guided by COMSOL multiphysics simulations. The films annealed under the optimized conditions reveal the presence of the orthorhombic phase, as confirmed by X-ray diffraction, electron backscatter diffraction, and transmission electron microscopy. Macroscopic polarization-electric field hysteresis loops show ferroelectric behavior, with saturation polarization of 12.8 mu C cm(-2), remnant polarization of 12.7 mu C cm(-2) and coercive field of 1.2 MV cm(-1). The films exhibit a wake-up effect that is attributed to the migration of point defects, such as oxygen vacancies, and/or a transition from nonferroelectric (monoclinic and tetragonal phase) to the ferroelectric orthorhombic phase. The capacitors demonstrate a stable polarization with an endurance of 6.0 x 10(5) cycles, demonstrating the potential of the NLA process for the fabrication of ferroelectric memory devices with high polarization, low coercive field, and high cycling stability.A.P.S.C. and M.C.I. contributed equally to this work. This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding Contract UIDB/04650/2020. This work has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No 958174 (M-ERA-NET3/0003/2021-NanOx4EStor). M. C. I. and C. G. acknowledge the financial support by a grant of the Ministry of Research, Innovation and Digitization, CNCS/CCCDI - UEFISCDI, project number COFUND-M-ERANET-3-NanOx4Estor, within PNCDI III and POC 332/390008/29.12.2020-SMIS 109522. The authors acknowledge the CERIC-ERIC Consortium for access to experimental facilities and financial support under proposals 20202037, 20202038, and 20192055. The authors would also like to thank Jose Santos for technical support in the Thin Film Laboratory at CF-UM-UP. J.L.M-D. thanks the ERC grant, EU-H2020-ERC-ADG #882929, EROS. And the Royal Academy of Engineering, grant CIET1819_24. MOH thanks the Herchel Smith foundation of Cambridge for a research fellowship. This work made use of the University of Cambridge Wolfson Electron Microscopy Suite

Long-latency modulation of motor cortex excitability by ipsilateral posterior inferior frontal gyrus and pre-supplementary motor area

The primary motor cortex (M1) is strongly influenced by several frontal regions. Dual-site transcranial magnetic stimulation (dsTMS) has highlighted the timing of early (<40 ms) prefrontal/premotor influences over M1. Here we used dsTMS to investigate, for the first time, longer-latency causal interactions of the posterior inferior frontal gyrus (pIFG) and pre-supplementary motor area (pre-SMA) with M1 at rest. A suprathreshold test stimulus (TS) was applied over M1 producing a motor-evoked potential (MEP) in the relaxed hand. Either a subthreshold or a suprathreshold conditioning stimulus (CS) was administered over ipsilateral pIFG/pre-SMA sites before the TS at different CS-TS inter-stimulus intervals (ISIs: 40-150 ms). Independently of intensity, CS over pIFG and pre-SMA (but not over a control site) inhibited MEPs at an ISI of 40 ms. The CS over pIFG produced a second peak of inhibition at an ISI of 150 ms. Additionally, facilitatory modulations were found at an ISI of 60 ms, with supra-but not subthreshold CS intensities. These findings suggest differential modulatory roles of pIFG and pre-SMA in M1 excitability. In particular, the pIFG-but not the pre-SMA-exerts intensity-dependent modulatory influences over M1 within the explored time window of 40-150 ms, evidencing fine-tuned control of M1 output

Individual Human Brain Areas Can Be Identified from Their Characteristic Spectral Activation Fingerprints

The human brain can be parcellated into diverse anatomical areas. We investigated whether rhythmic brain activity in these areas is characteristic and can be used for automatic classification. To this end, resting-state MEG data of 22 healthy adults was analysed. Power spectra of 1-s long data segments for atlas-defined brain areas were clustered into spectral profiles (“fingerprints”), using k-means and Gaussian mixture (GM) modelling. We demonstrate that individual areas can be identified from these spectral profiles with high accuracy. Our results suggest that each brain area engages in different spectral modes that are characteristic for individual areas. Clustering of brain areas according to similarity of spectral profiles reveals well-known brain networks. Furthermore, we demonstrate task-specific modulations of auditory spectral profiles during auditory processing. These findings have important implications for the classification of regional spectral activity and allow for novel approaches in neuroimaging and neurostimulation in health and disease

Long Lasting Modulation of Cortical Oscillations after Continuous Theta Burst Transcranial Magnetic Stimulation

Transcranial magnetic theta burst stimulation (TBS) differs from other high-frequency rTMS protocols because it induces plastic changes up to an hour despite lower stimulus intensity and shorter duration of stimulation. However, the effects of TBS on neuronal oscillations remain unclear. In this study, we used electroencephalography (EEG) to investigate changes of neuronal oscillations after continuous TBS (cTBS), the protocol that emulates long-term depression (LTD) form of synaptic plasticity. We randomly divided 26 healthy humans into two groups receiving either Active or Sham cTBS as control over the left primary motor cortex (M1). Post-cTBS aftereffects were assessed with behavioural measurements at rest using motor evoked potentials (MEPs) and at active state during the execution of a choice reaction time (RT) task in combination with continuous electrophysiological recordings. The cTBS-induced EEG oscillations were assessed using event-related power (ERPow), which reflected regional oscillatory activity of neural assemblies of θ (4–7.5 Hz), low α (8–9.5 Hz), µ (10–12.5 Hz), low β (13–19.5 Hz), and high β (20–30 Hz) brain rhythms. Results revealed 20-min suppression of MEPs and at least 30-min increase of ERPow modulation, suggesting that besides MEPs, EEG has the potential to provide an accurate cortical readout to assess cortical excitability and to investigate the interference of cortical oscillations in the human brain post-cTBS. We also observed a predominant modulation of β frequency band, supporting the hypothesis that cTBS acts more on cortical level. Theta oscillations were also modulated during rest implying the involvement of independent cortical theta generators over the motor network post cTBS. This work provided more insights into the underlying mechanisms of cTBS, providing a possible link between synchronised neural oscillations and LTD in humans