Hierarchically Structured Magnetic Nanoconstructs with Enhanced Relaxivity and Cooperative Tumor Accumulation

Iron oxide nanoparticles are formidable multifunctional systems capable of contrast enhancement in magnetic resonance imaging, guidance under remote fields, heat generation, and biodegradation. Yet, this potential is underutilized in that each function manifests at different nanoparticle sizes. Here, sub‐micrometer discoidal magnetic nanoconstructs are realized by confining 5 nm ultra‐small super‐paramagnetic iron oxide nanoparticles (USPIOs) within two different mesoporous structures, made out of silicon and polymers. These nanoconstructs exhibit transversal relaxivities up to ≈10 times (r ₂ ≈ 835 mm ^?1 s^?1) higher than conventional USPIOs and, under external magnetic fields, collectively cooperate to amplify tumor accumulation. The boost in r ₂ relaxivity arises from the formation of mesoscopic USPIO clusters within the porous matrix, inducing a local reduction in water molecule mobility as demonstrated via molecular dynamics simulations. The cooperative accumulation under static magnetic field derives from the large amount of iron that can be loaded per nanoconstuct (up to ≈65 fg) and the consequential generation of significant inter‐particle magnetic dipole interactions. In tumor bearing mice, the silicon‐based nanoconstructs provide MRI contrast enhancement at much smaller doses of iron (≈0.5 mg of Fe kg^?1 animal) as compared to current practice.     

State‐of‐the‐Art Neutral Tint Multichromophoric Polymers for High‐Contrast See‐Through Electrochromic Devices

Two new multichromophoric electrochromic polymers featuring a conjugated EDOT/ProDOT copolymer backbone (PXDOT) and a reversible Weitz‐type redox active small molecule electrochrome (WTE) tethered to the conjugated chain are reported here. The careful design of the WTEs provides a highly reversible redox behavior with a colorless red switching that complements the colorless blue switching of the conjugated backbone. Subtractive color mixing successfully provides high performing solution processable polymeric layers with colorless neutral tint switchable limiting states for application in see‐through electrochromic devices. Design, synthesis, comprehensive chemical and spectroelectrochemical characterization as well as the preparation of a proof‐of‐concept device are discussed.     

Graphite Oxide and Aromatic Amines: Size Matters

Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molecules prefer to covalently connect to the graphene oxide matrix via chemical grafting, while napthalene amine molecules bind with the graphene oxide surface through π–π interactions. The presence of intercalated aromatic molecules between the graphene oxide layers is demonstrated by X‐ray diffraction, while the type of interaction between graphene oxide and polycyclic organic molecules is elucidated by X‐ray photoelectron spectroscopy. Combined quantum mechanical and molecular mechanical calculations describe the intercalation mechanism and the aniline grafting, rationalizing the experimental data. The present work opens new perspectives for the interaction of various aromatic molecules with graphite oxide and the so‐called “intercalation chemistry”.     

Stochastic algorithms for robustness of control performances

In recent years, there has been a growing interest in developing statistical learning methods to provide approximate solutions to “difficult” control problems. In particular, randomized algorithms have become a very popular tool used for stability and performance analysis as well as for design of control systems. However, as randomized algorithms provide an efficient solution procedure to the “intractable” problems, stochastic methods bring closer to understanding the properties of the real systems. The topic of this paper is the use of stochastic methods in order to solve the problem of control robustness: the case of parametric stochastic uncertainty is considered. Necessary concepts regarding stochastic control theory and stochastic differential equations are introduced. Then a convergence analysis is provided by means of the Chernoff bounds, which guarantees robustness in mean and in probability. As an illustration, the robustness of control performances of example control systems is computed.     

On the collective sort problem for distributed tuple spaces

In systems coordinated with a distributed set of tuple spaces, it is crucial to assist agents in retrieving the tuples they are interested in. This can be achieved by sorting techniques that group similar tuples together in the same tuple space, so that the position of a tuple can be inferred by similarity. Accordingly, we formulate the collective sort problem for distributed tuple spaces, where a set of agents is in charge of moving tuples up to a complete sort has been reached, namely, each of the N tuple spaces aggregate tuples belonging to one of the N kinds available. After pointing out the requirements for effectively tackling this problem, we propose a self-organizing solution resembling brood sorting performed by ants. This is based on simple agents that perform partial observations and accordingly take decisions on tuple movement. Convergence is addressed by a fully adaptive method for simulated annealing, based on noise tuples inserted and removed by agents on a need basis so as to avoid sub-optimal sorting. Emergence of sorting properties and scalability are evaluated through stochastic simulations.     

Simulating Ramsey-Type Fringes in a Pulsed Microwave-Driven Classical Josephson Junction

We present evidence for a close analogy between the nonlinear behaviour of a pulsed microwave-driven Josephson junction at low temperature and the experimentally observed behaviour of Josephson systems operated below the quantum transition temperature under similar conditions. We specifically address observations of Ramsey-type fringe oscillations, which can be understood in classical nonlinear dynamics as results of slow transient oscillations in a pulsed microwave environment. Simulations are conducted to mimic experimental measurements by recording the statistics of microwave-induced escape events from the anharmonic potential well of a zero-voltage state. Observations consistent with experimentally obtained Ramsey-type oscillations are found in the classical model. An erratum to this article can be found at     

A Lyapunov method for stability analysis of piecewise-affine systems over non-invariant domains

This paper analyses stability of discrete-time piecewise-affine systems, defined on possibly non-invariant domains, taking into account the possible presence of multiple dynamics in each of the polytopic regions of the system. An algorithm based on linear programming is proposed, in order to prove exponential stability of the origin and to find a positively invariant estimate of its region of attraction. The results are based on the definition of a piecewise-affine Lyapunov function, which is in general discontinuous on the boundaries of the regions. The proposed method is proven to lead to feasible solutions in a broader range of cases as compared to a previously proposed approach. Two numerical examples are shown, among which a case where the proposed method is applied to a closed-loop system, to which model predictive control was applied without a-priori guarantee of stability.