A selection and targeting framework of cortical locations for line-scanning fMRI.

Depth-resolved functional magnetic resonance imaging (fMRI) is an emerging field growing in popularity given the potential of separating signals from different computational processes in cerebral cortex. Conventional acquisition schemes suffer from low spatial and temporal resolutions. Line-scanning methods allow depth-resolved fMRI by sacrificing spatial coverage to sample blood oxygenated level-dependent (BOLD) responses at ultra-high temporal and spatial resolution. For neuroscience applications, it is critical to be able to place the line accurately to (1) sample the right neural population and (2) target that neural population with tailored stimuli or tasks. To this end, we devised a multi-session framework where a target cortical location is selected based on anatomical and functional properties. The line is then positioned according to this information in a separate second session, and we tailor the experiment to focus on the target location. Anatomically, the precision of the line placement was confirmed by projecting a nominal representation of the acquired line back onto the surface. Functional estimates of neural selectivities in the line, as quantified by a visual population-receptive field model, resembled the target selectivities well for most subjects. This functional precision was quantified in detail by estimating the distance between the visual field location of the targeted vertex and the location in visual cortex (V1) that most closely resembled the line-scanning estimates; this distance was on average ~5.5 mm. Given the dimensions of the line, differences in acquisition, session, and stimulus design, this validates that line-scanning can be used to probe local neural sensitivities across sessions. In summary, we present an accurate framework for line-scanning MRI; we believe such a framework is required to harness the full potential of line-scanning and maximize its utility. Furthermore, this approach bridges canonical fMRI experiments with electrophysiological experiments, which in turn allows novel avenues for studying human physiology non-invasively.

Post-Growth Dynamics and Growth Modeling of Organic Semiconductor Thin Films.

The ability to control the properties of organic thin films is crucial for obtaining highly performant thin-film devices. However, thin films may experience post-growth processes, even when the most sophisticated and controlled growth techniques such as organic molecular beam epitaxy (OMBE) are used. Such processes can modify the film structure and morphology and, thus, the film properties ultimately affecting device performances. For this reason, probing the occurrence of post-growth evolution is essential. Equally importantly, the processes responsible for this evolution should be addressed in view of finding a strategy to control and, possibly, leverage them for driving film properties. Here, nickel-tetraphenylporphyrin (NiTPP) thin films grown by OMBE on highly oriented pyrolytic graphite (HOPG) are selected as an exemplary system exhibiting a remarkable post-growth morphology evolution consistent with Ostwald-like ripening. To quantitatively describe the growth, the height-height correlation function (HHCF) analysis of the atomic force microscopy (AFM) images is carried out, clarifying the role of the post-growth evolution as an integral part of the whole growth process. The set of scaling exponents obtained confirms that the growth is mainly driven by diffusion combined with the presence of step-edge barriers, in agreement with the observed ripening phenomenon. Finally, the results together with the overall approach adopted demonstrate the reliability of the HHCF analysis in systems displaying post-growth evolution.

Towards functional spin-echo BOLD line-scanning in humans at 7T.

OBJECTIVE: Neurons cluster into sub-millimeter spatial structures and neural activity occurs at millisecond resolutions; hence, ultimately, high spatial and high temporal resolutions are required for functional MRI. In this work, we implemented a spin-echo line-scanning (SELINE) sequence to use in high spatial and temporal resolution fMRI. MATERIALS AND METHODS: A line is formed by simply rotating the spin-echo refocusing gradient to a plane perpendicular to the excited slice and by removing the phase-encoding gradient. This technique promises a combination of high spatial and temporal resolution (250 µm, 500 ms) and microvascular specificity of functional responses. We compared SELINE data to a corresponding gradient-echo version (GELINE). RESULTS: We demonstrate that SELINE showed much-improved line selection (i.e. a sharper line profile) compared to GELINE, albeit at the cost of a significant drop in functional sensitivity. DISCUSSION: This low functional sensitivity needs to be addressed before SELINE can be applied for neuroscientific purposes.

Robust high spatio-temporal line-scanning fMRI in humans at 7T using multi-echo readouts, denoising and prospective motion correction.

BACKGROUND: Functional magnetic resonance imaging (fMRI), typically using blood oxygenation level-dependent (BOLD) contrast weighted imaging, allows the study of brain function with millimeter spatial resolution and temporal resolution of one to a few seconds. At a mesoscopic scale, neurons in the human brain are spatially organized in structures with dimensions of hundreds of micrometers, while they communicate at the millisecond timescale. For this reason, it is important to develop an fMRI method with simultaneous high spatial and temporal resolution. Line-scanning promises to reach this goal at the cost of volume coverage. NEW METHOD: Here, we release a comprehensive update to human line-scanning fMRI. First, we investigated multi-echo line-scanning with five different protocols varying the number of echoes and readout bandwidth while keeping the TR constant. In these, we compared different echo combination approaches in terms of BOLD activation (sensitivity) and temporal signal-to-noise ratio. Second, we implemented an adaptation of NOise reduction with DIstribution Corrected principal component analysis (NORDIC) thermal noise removal for line-scanning fMRI data. Finally, we tested three image-based navigators for motion correction and investigated different ways of performing fMRI analysis on the timecourses which were influenced by the insertion of the navigators themselves. RESULTS: The presented improvements are relatively straightforward to implement; multi-echo readout and NORDIC denoising together, significantly improve data quality in terms of tSNR and t-statistical values, while motion correction makes line-scanning fMRI more robust. COMPARISON WITH EXISTING METHODS: Multi-echo acquisitions and denoising have previously been applied in 3D magnetic resonance imaging. Their combination and application to 1D line-scanning is novel. The current proposed method greatly outperforms the previous line-scanning acquisitions with single-echo acquisition, in terms of tSNR (4.0 for single-echo line-scanning and 36.2 for NORDIC-denoised multi-echo) and t-statistical values (3.8 for single-echo line-scanning and 25.1 for NORDIC-denoised multi-echo line-scanning). CONCLUSIONS: Line-scanning fMRI was advanced compared to its previous implementation in order to improve sensitivity and reliability. The improved line-scanning acquisition could be used, in the future, for neuroscientific and clinical applications.

Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.

Advances in resting state fMRI acquisitions for functional connectomics.

Resting state functional magnetic resonance imaging (rs-fMRI) is based on spontaneous fluctuations in the blood oxygen level dependent (BOLD) signal, which occur simultaneously in different brain regions, without the subject performing an explicit task. The low-frequency oscillations of the rs-fMRI signal demonstrate an intrinsic spatiotemporal organization in the brain (brain networks) that may relate to the underlying neural activity. In this review article, we briefly describe the current acquisition techniques for rs-fMRI data, from the most common approaches for resting state acquisition strategies, to more recent investigations with dedicated hardware and ultra-high fields. Specific sequences that allow very fast acquisitions, or multiple echoes, are discussed next. We then consider how acquisition methods weighted towards specific parts of the BOLD signal, like the Cerebral Blood Flow (CBF) or Volume (CBV), can provide more spatially specific network information. These approaches are being developed alongside the commonly used BOLD-weighted acquisitions. Finally, specific applications of rs-fMRI to challenging regions such as the laminae in the neocortex, and the networks within the large areas of subcortical white matter regions are discussed. We finish the review with recommendations for acquisition strategies for a range of typical applications of resting state fMRI.

A line through the brain: implementation of human line-scanning at 7T for ultra-high spatiotemporal resolution fMRI.

Functional magnetic resonance imaging (fMRI) is a widely used tool in neuroscience to detect neurally evoked responses, e.g. the blood oxygenation level-dependent (BOLD) signal. Typically, BOLD fMRI has millimeter spatial resolution and temporal resolution of one to few seconds. To study the sub-millimeter structures and activity of the cortical gray matter, the field needs an fMRI method with high spatial and temporal resolution. Line-scanning fMRI achieves very high spatial resolution and high sampling rate, at the cost of a sacrifice in volume coverage. Here, we present a human line-scanning implementation on a 7T MRI system. First, we investigate the quality of the saturation pulses that suppress MR signal outside the line. Second, we established the best coil combination for reconstruction. Finally, we applied the line-scanning method in the occipital lobe during a visual stimulation task, showing BOLD responses along cortical depth, every 250 µm with a 200 ms repetition time (TR). We found a good correspondence of t-statistics values with 2D gradient-echo echo planar imaging (GE-EPI) BOLD fMRI data with the same temporal resolution and voxel volume (R = 0.6 ± 0.2). In summary, we demonstrate the feasibility of line-scanning in humans and this opens line-scanning fMRI for applications in cognitive and clinical neuroscience.

Nature of Optical Excitations in Porphyrin Crystals: A Joint Experimental and Theoretical Study.

The nature of optical excitations and the spatial extent of excitons in organic semiconductors, both of which determine exciton diffusion and carrier mobilities, are key factors for the proper understanding and tuning of material performances. Using a combined experimental and theoretical approach, we investigate the excitonic properties of meso-tetraphenyl porphyrin-Zn(II) crystals. We find that several bands contribute to the optical absorption spectra, beyond the four main ones considered here as the analogue to the four frontier molecular orbitals of the Gouterman model commonly adopted for the isolated molecule. By using many-body perturbation theory in the GW and Bethe-Salpeter equation approach, we interpret the experimental large optical anisotropy as being due to the interplay between long- and short-range intermolecular interactions. In addition, both localized and delocalized excitons in the π-stacking direction are demonstrated to determine the optical response, in agreement with recent experimental observations reported for organic crystals with similar molecular packing.

Comparing hand movement rate dependence of cerebral blood volume and BOLD responses at 7T.

Functional magnetic resonance imaging (fMRI) based on the Blood Oxygenation Level Dependent (BOLD) contrast takes advantage of the coupling between neuronal activity and the hemodynamics to allow a non-invasive localisation of the neuronal activity. In general, fMRI experiments assume a linear relationship between neuronal activation and the observed hemodynamics. However, the relationship between BOLD responses, neuronal activity, and behaviour are often nonlinear. In addition, the nonlinearity between BOLD responses and behaviour may be related to neuronal process rather than a neurovascular uncoupling. Further, part of the nonlinearity may be driven by vascular nonlinearity effects in particular from large vessel contributions. fMRI based on cerebral blood volume (CBV), promises a higher microvascular specificity, potentially without vascular nonlinearity effects and reduced contamination of the large draining vessels compared to BOLD. In this study, we aimed to investigate differences in BOLD and VASO-CBV signal changes during a hand movement task over a broad range of movement rates. We used a double readout 3D-EPI sequence at 7T to simultaneously measure VASO-CBV and BOLD responses in the sensorimotor cortex. The measured BOLD and VASO-CBV responses increased very similarly in a nonlinear fashion, plateauing for movement rates larger than 1 Hz. Our findings show a tight relationship between BOLD and VASO-CBV responses, indicating that the overall interplay of CBV and BOLD responses are similar for the assessed range of movement rates. These results suggest that the observed nonlinearity of neuronal origin is already present in VASO-CBV measurements, and consequently shows relatively unchanged BOLD responses.

Pushing functional MRI spatial and temporal resolution further: High-density receive arrays combined with shot-selective 2D CAIPIRINHA for 3D echo-planar imaging at 7 T.

To be able to examine dynamic and detailed brain functions, the spatial and temporal resolution of 7 T MRI needs to improve. In this study, it was investigated whether submillimeter multishot 3D EPI fMRI scans, acquired with high-density receive arrays, can benefit from a 2D CAIPIRINHA sampling pattern, in terms of noise amplification (g-factor), temporal SNR and fMRI sensitivity. High-density receive arrays were combined with a shot-selective 2D CAIPIRINHA implementation for multishot 3D EPI sequences at 7 T. In this implementation, in contrast to conventional inclusion of extra kz gradient blips, specific EPI shots are left out to create a CAIPIRINHA shift and reduction of scan time. First, the implementation of the CAIPIRINHA sequence was evaluated with a standard receive setup by acquiring submillimeter whole brain T2 *-weighted anatomy images. Second, the CAIPIRINHA sequence was combined with high-density receive arrays to push the temporal resolution of submillimeter 3D EPI fMRI scans of the visual cortex. Results show that the shot-selective 2D CAIPIRINHA sequence enables a reduction in scan time for 0.5 mm isotropic 3D EPI T2 *-weighted anatomy scans by a factor of 4 compared with earlier reports. The use of the 2D CAIPIRINHA implementation in combination with high-density receive arrays, enhances the image quality of submillimeter 3D EPI scans of the visual cortex at high acceleration as compared to conventional SENSE. Both the g-factor and temporal SNR improved, resulting in a method that is more sensitive to the fMRI signal. Using this method, it is possible to acquire submillimeter single volume 3D EPI scans of the visual cortex in a subsecond timeframe. Overall, high-density receive arrays in combination with shot-selective 2D CAIPIRINHA for 3D EPI scans prove to be valuable for reducing the scan time of submillimeter MRI acquisitions.

Control of post-growth processes for the selection of metallo-tetraphenylporphyrin nanowires.

Controlling self-organization of small organic molecules in nanostructures with a desired shape and size is one of the main challenges in organic nanoelectronics. Here, a strategy for selectively growing uniaxially aligned nanowires of meso-tetraphenyl porphyrin-Zn(ii) (ZnTPP) is presented. ZnTPP is deposited on an organic single crystal, namely potassium hydrogen phthalate, by organic molecular beam epitaxy. The films typically display a rather rich surface morphology, characterized by the presence of nanowires and other nm-sized aggregates, most of them unstable over time. Post-growth processes occurring via quasi-Ostwald ripening both in air and in vacuum demonstrate an aging protocol in vacuum as a tool for the selection of ZnTPP nanowires, whose morphology and uniaxial orientation are demonstrated to be led by organic epitaxy. The ability of growing ZnTPP nanowires with a unique crystal structure and precise orientation gives the chance to observe the intrinsic optical anisotropy of the triclinic polymorph of ZnTPP crystal and establishes the role of intermolecular interactions, providing new perspectives in the study of the intrinsic physical properties of ZnTPP crystals.

Patterned growth of crystalline organic heterostructures.

Organic droplet epitaxy is presented as a method for growing nanopatterned crystalline heterostructures, thanks to the transport of molecules of an amorphous first-layer on top of a crystalline second-layer, where they form an epitaxial interface. Such heterostructures may be transferred to any substrates, raising particular interest for applications (e.g., for organic photovoltaics), where crystallinity and nanopatterning constitute well recognized advantages.

Grazing-incidence X-ray diffraction study of rubrene epitaxial thin films.

The growth of organic semiconductors as thin films with good and controlled electrical performances is nowadays one of the main tasks in the field of organic semiconductor-based electronic devices. In particular it is often required to grow highly crystalline and precisely oriented thin films. Here, thanks to grazing-incidence X-ray diffraction measurements carried out at the ELETTRA synchrotron facility, it is shown that rubrene thin films deposited by organic molecular beam epitaxy on the surface of tetracene single crystals have the structure of the known orthorhombic polymorph, with the (2 0 0) plane parallel to the substrate surface. Moreover, the exact epitaxial relationship between the film and the substrate crystalline structures is determined, demonstrating the presence of a unique in-plane orientation of the overlayer.

Exciton-phonon coupling in molecular crystals: synergy between two intramolecular vibrational modes in quaterthiophene single crystals.

Exciton-phonon (EP) coupling in molecular crystals is investigated in the case where two intramolecular vibrational modes are involved and a theoretical model is presented which applies when one of the modes is strongly coupled to crystal excitons. The model is used to simulate the low energy portion of the absorption spectra of quaterthiophene (4T) single crystals, for which we find it appropriate to consider a low energy vibrational mode at 161 cm(-1) and an effective strongly coupled high energy mode at 1470 cm(-1). Our numerical results demonstrate that the high energy mode renormalizes the excitonic band, thereby strongly affecting the environment seen by the low energy mode and the overall EP coupling regime. Numerical simulations also confirm the existence of the new coupling regimes "intermediate-I" and "strong-I" already introduced for oligothiophene aggregates [Spano et al., J. Chem. Phys. 127, 184703 (2007)], which arise as a consequence of the large effective mass of low energy excitons in 4T crystals. Comparison with experimental high resolution absorption spectra is also reported and shown to support the model predictions.

Polymorphism and phonon dynamics of alpha-quaterthiophene.

Low-frequency (10-150 cm(-1)) Raman spectra of the low-temperature (LT) and high-temperature (HT) polymorphs of the organic semiconductor alpha-quaterthiophene at 300 and 10 K are reported. Polarized spectra, assisted by quasi-harmonic lattice dynamics (QHLD) calculations, allow characterization of the lattice phonon dynamics and identification of the two phases spectroscopically. The experimental data can be explained by taking into account the coupling between intermolecular (lattice) and low-frequency intramolecular modes. Finally, Raman mapping is used to investigate the phase purity.