Project description:We report the synthesis and characterization of covalent organic frameworks (COFs) incorporating thiophene-based building blocks. We show that these are amenable to reticular synthesis, and that bent ditopic monomers, such as 2,5-thiophenediboronic acid, are defect-prone building blocks that are susceptible to synthetic variations during COF synthesis. The synthesis and characterization of an unusual charge transfer complex between thieno[3,2-b]thiophene-2,5-diboronic acid and tetracyanoquinodimethane enabled by the unique COF architecture is also presented. Together, these results delineate important synthetic advances toward the implementation of COFs in electronic devices.
Project description:BackgroundSynergy modules have been used to describe activation of lower limb muscles during locomotion and hence to understand how the system controls movement. Walking and running have been shown shared synergy patterns suggesting common motor control of both symmetrical gaits. Unilateral skipping, an equivalent gait to the quadrupedal gallop in humans, has been defined as the third locomotion paradigm but the use by humans is limited due to its high metabolic cost. Synergies in skipping have been little investigated. In particular, to the best of our knowledge, the joint study of both trailing and leading limbs has never been addressed before.Research questionHow are organized muscle activation patterns in unilateral skipping? Are they organized in the same way that in symmetrical gaits? If yes, which are the muscle activation patterns in skipping that make it a different gait to walking or running? In the present research, we investigate if there are shared control strategies for all gaits in locomotion. Addressing these questions in terms of muscle synergies could suggest possible determinants of the scarce use of unilateral skipping in humans.MethodsElectromyographic data of fourteen bilateral muscles were collected from volunteers while performing walking, running and unilateral skipping on a treadmill. Also, spatiotemporal gait parameters were computed from 3D kinematics. The modular composition and activation timing extracted by non-negative matrix factorization were analyzed to detect similarities and differences among symmetrical gaits and unilateral skipping.ResultsSynergy modules showed high similarity throughout the different gaits and between trailing and leading limbs during unilateral skipping. The synergy associated with the propulsion force operated by calf muscles was anticipated in bouncing gaits. Temporal features of synergies in the leading leg were very similar to those observed for running. The different role of trailing and leading legs in unilateral skipping was reflected by the different timing in two modules. Activation for weight acceptance was anticipated and extended in the trailing leg, preparing the body for landing impact after the flight phase. A different behaviour was detected in the leading leg, which only deals with a pendular weight transference.SignificanceThe evidence gathered in this work supports the hypothesis of shared modules among symmetrical and asymmetrical gaits, suggesting a common motor control despite of the infrequent use of unilateral skipping in humans. Unilateral skipping results from phase-shifted activation of similar muscular groups used in symmetrical gaits, without the need for new muscular groups. The high and anticipated muscle activation in the trailing leg for landing could be the key distinctive event of unilateral skipping.
Project description:Controlling symmetrical or asymmetrical growth has allowed a series of novel nanomaterials with prominent physicochemical properties to be produced. However, precise and continuous size growth based on a preserved template has long been a challenging pursuit, yet little has been achieved in terms of manipulation at the atomic level. Here, a correlated silver cluster series has been established, enabling atomically precise manipulation of symmetrical and asymmetrical surface structure expansions of metal nanoclusters. Specifically, the C 3-axisymmetric Ag29(BDTA)12(PPh3)4 nanocluster underwent symmetrical and asymmetrical surface structure expansions via an acid-mediated synthetic procedure, giving rise to C 3-axisymmetric Ag32(BDTA)12(PPh3)10 and C 1-axisymmetric Ag33(BDTA)12(PPh3)11, respectively. In addition, structural transformations, including structural degradation from Ag32 to Ag29 and asymmetrical structural expansion from Ag32 to Ag33, were rationalized theoretically. More importantly, the asymmetrically structured Ag33 nanoclusters followed a chiral crystallization mode, and their crystals displayed high optical activity, derived from CD and CPL characterization. This work not only provides an important model for unlocking the symmetrical/asymmetrical size growth mechanism at the atomic level but also pioneers a promising approach to activate the optical activity of cluster-based nanomaterials.
Project description:A series of three novel donor-acceptor systems based on C(3)-malononitrile-substituted phenothiazines was synthesised in good overall yields and their thermal, spectroscopic, and electrochemical properties were characterised. The compounds were prepared through a sequence of Ullmann-coupling, Vilsmeier-Haack formylation and Knoevenagel-condensation, followed by Suzuki-coupling reactions for introduction of aryl substitutents at C(7) position of the phenothiazine. The introduction of a donor unit at the C(7) position exhibited a weak impact on the optical and electrochemical characteristics of the compounds and led to amorphous films with bulk hole mobilities in the typical range reported for phenothiazines, despite the higher charge delocalisation as attested by computational studies. In contrast, highly ordered films were formed when using the C(7)-unsubstituted 3-malononitrile phenothiazine, exhibiting an outstanding mobility of 1 × 10-3 cm2 V-1 s-1, the highest reported for this class of compounds. Computational conformational analysis of the new phenothizanes suggested that free rotation of the substitutents at the C(7) position suppresses the ordering of the system, thereby hampering suitable packing of the new materials needed for high charge carrier mobility.
Project description:The removal of sulfur compounds, particularly thiophene derivatives, from oil is crucial due to concerns about environmental issues. Therefore, the deep desulfurization of transportation fuels is currently an urgent problem, and numerous attempts have been made in this direction. Membrane-based desulfurization can be a good alternative to the traditional hydrodesulfurization method, which has several limitations. In this work, the use of membranes containing a metal-organic framework, MOF-5, doped with transition metals (Ag, Cu, Ni), in the adsorptive desulfurization process was studied. The efficiency of membranes was evaluated based on selective removal of thiophene and dibenzothiophene from model oil. Characterization techniques, including scanning electron microscopic (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA), confirmed the successful synthesis and incorporation of metal-organic frameworks (MOFs) into mixed matrix membranes (MMMs). Desulfurization experiments showed that MOF-5/Ag exhibited the highest thiophene adsorption efficiency (86.8%), outperforming MOF-5/Cu and MOF-5/Ni. The enhanced performance is attributed to the strong interaction between silver and sulfur. These findings demonstrate the potential of MOF-based MMMs for efficient and selective desulfurization, offering a viable alternative to traditional hydrodesulfurization (HDS) methods.
Project description:The versatility of organic molecules generates a rich design space for organic semiconductors (OSCs) considered for electronics applications. Offering unparalleled promise for materials discovery, the vastness of this design space also dictates efficient search strategies. Here, we present an active machine learning (AML) approach that explores an unlimited search space through consecutive application of molecular morphing operations. Evaluating the suitability of OSC candidates on the basis of charge injection and mobility descriptors, the approach successively queries predictive-quality first-principles calculations to build a refining surrogate model. The AML approach is optimized in a truncated test space, providing deep methodological insight by visualizing it as a chemical space network. Significantly outperforming a conventional computational funnel, the optimized AML approach rapidly identifies well-known and hitherto unknown molecular OSC candidates with superior charge conduction properties. Most importantly, it constantly finds further candidates with highest efficiency while continuing its exploration of the endless design space.
Project description:Organic semiconductors have found a broad range of application in areas such as light emission, photovoltaics, and optoelectronics. The active components in such devices are based on molecular and polymeric organic semiconductors, where the density of states is generally determined by the disordered nature of the molecular solid rather than energy bands. Inevitably, there exist states within the energy gap which may include tail states, deep traps caused by unavoidable impurities and defects, as well as intermolecular states due to (radiative) charge transfer states. In this Perspective, we first summarize methods to determine the absorption features due to the subgap states. We then explain how subgap states can be parametrized based upon the subgap spectral line shapes. We finally describe the role of subgap states in the performance metrics of organic semiconductor devices from a thermodynamic viewpoint.
Project description:Polarization-sensitive photodetectors based on anisotropic semiconductors sense both the intensity and polarization state information without extra optical components. Here, a self-powered organic photodetector (OPD) composed of intrinsically stretchable polymer donor PNTB6-Cl and non-fullerene acceptor Y6 is reported. The PNTB6-Cl:Y6 photoactive film accommodates a remarkable 100% strain without fracture, exhibiting a high optical anisotropy of 1.8 after strain alignment. The resulting OPD not only shows an impressive faint-light detection capability (high spectral responsivity of 0.45 A W-1 and high specific detectivity of 1012 Jones), but also has a high anisotropic responsivity ratio of 1.42 under the illumination of parallel and traversed polarized light. To the best of the authors' knowledge, both the detector performance and polarization features are among the best-performing OPDs and polarization-sensitive photodetectors. As a proof-of-concept, polarization-sensitive OPDs are also utilized to set up a polarimetric imaging system and full-Stokes polarimeter. This work explores the potential of highly stretchable organic semiconductors for state-of-art polarization imaging and spectroscopy applications.
Project description:Modularity (Muscle synergy) is the concept that has been used to answer the question of how the central nervous system (CNS) coordinates the body's high degrees of freedom. This study aimed to investigate the trunk muscle synergies in symmetrical and asymmetrical positions. Fourteen healthy males participated. Electromyographical activities of 16 muscles were recorded during maximum voluntary isometric contraction (MVIC) in six main directions with two repetitions and maximum voluntary isometric extension (MVIE) of the trunk in 23 different three-dimensional trunk positions. Muscle synergies were extracted separately using non-negative matrix factorization during MVIC (with one/two repetitions) and MVIE. The effect of position changes on synergies was investigated using response surface models and the Pearson correlation coefficient. The findings show that 6 synergies for 6 directions MVIC and 2 synergies for MVIE are suitable with the variance accounted for of 99.65 ± 0.65 96 and 94.14 ± 1.59, respectively. Trial repetition does not affect the synergies. In Conclusion, during the same activity in different positions and trials, the synergy of the main activity is preserved. These show the stability of synergies and their dependence on the activity type. This stability may help to determine the main damage caused and provide appropriate treatment protocol for trunk injuries.
Project description:Organic semiconductors have great potential for producing hydrogen in a sustainable and economically-viable manner because they rely on readily available materials with highly tunable properties. We demonstrate here the relevance of heterojunctions to the construction of H2-evolving photocathodes, exclusively based on earth-abundant elements. Boron subnaphthalocyanine chloride proved a very promising acceptor in that perspective. It absorbs a part of the solar spectrum complementary to ?-sexithiophene as a donor, thus generating large photocurrents and providing a record onset potential for light-driven H2 evolution under acidic aqueous conditions using a nanoparticulate amorphous molybdenum sulfide catalyst.