The notable transformation of the electronic properties of transition-metal dichalcogenides (TMDs) when reduced to a single X-M-X plane (X: chalcogen; M: metal) [1] makes them suitable for flexible, innovative optoelectronic devices, [2][3][4] and transistors. [5] Like graphene, few-layer TMDs can also withstand surprisingly large mechanical deformations, [6][7][8][9] which, coupled to the material's electronic structure, would enable the observation of nondissipative topological transport, provided a periodic modulation of strain is attained. [10][11][12][13] TMD monolayers (MLs) and nanostructures are also important for their catalytic role in the cost-effective production of hydrogen. [14][15][16] These examples share the need to achieve spatial control of the material's properties, over sample regions with size ranging from the nano [14,16] to the micrometer [16] scale lengths.In this study, we present a route toward the patterning of TMDs based on the effects of low-energy proton irradiation [17] on the structural and electronic properties of bulk WS 2 , WSe 2 , WTe 2 , MoS 2 , MoSe 2 , and MoTe 2 . Suitable irradiation conditions trigger the production and accumulation of H 2 just beneath the first X-M-X basal plane, leading to the localized exfoliation of the topmost monolayer and to the formation of spherically shaped domes. Structural and optical characterizations confirm that these domes are typically one ML-thick and contain H 2 at pressures in the 10-100 atm range, depending on their size. Such high pressures induce strong and complex strain fields acting on the curved X-M-X planes, that are evaluated by means of a mechanical model. The domes' morphological characteristics can be tuned by lithographically controlling the area of the sample basal plane participating in the hydrogen production process. This results in the unprecedented fabrication of robust domes with controlled position/density and sizes tunable from the nanometer to the micrometer scale, that, by virtue of their inherently strained nature and geometry, might prompt a variety of applications.The samples, consisting of thick (tens to hundreds of MLs) TMD flakes, were obtained by mechanical exfoliation, deposited on Si substrates, and afterwards proton-irradiated using a Kaufman source (see the Experimental Methods). Differently from the other works in the literature concerning protonirradiation of TMDs-where beams with energies ≥10 5 eV are used, [18] aiming at the controlled formation of defects in the irradiated samples-here we irradiate the flakes with low energy At the few-atom-thick limit, transition-metal dichalcogenides (TMDs) exhibit strongly interconnected structural and optoelectronic properties. The possibility to tailor the latter by controlling the former is expected to have a great impact on applied and fundamental research. As shown here, proton irradiation deeply affects the surface morphology of bulk TMD crystals. Protons penetrate the top layer, resulting in the production and progressive accumulation of molecular hydr...

Different charged colloidal particles have been shown to be able to self-assemble, when mixed in an aqueous solvent with oppositely charged linear polyelectrolytes, forming long-lived finite-size mesoscopic aggregates. On increasing the polyelectrolyte content, with the progressive reduction of the net charge of the primary polyelectrolyte-decorated particles, larger and larger clusters are observed. Close to the isoelectric point, where the charge of the adsorbed polyelectrolytes neutralizes the original charge of the particles' surface, the aggregates reach their maximum size, while beyond this point any further increase of the polyelectrolyte-particle charge ratio causes the formation of aggregates whose size is progressively reduced. This re-entrant condensation behavior is accompanied by a significant overcharging. Overcharging, or charge inversion, occurs when more polyelectrolyte chains adsorb on a particle than are needed to neutralize its original charge so that, eventually, the sign of the net charge of the polymer-decorated particle is inverted. The stability of the finite-size long-lived clusters that this aggregation process yields results from a fine balance between long-range repulsive and short-range attractive interactions, both of electrostatic nature. For the latter, besides the ubiquitous dispersion forces, whose supply becomes relevant only at high ionic strength, the main contribution appears due to the non-uniform correlated distribution of the charge on the surface of the polyelectrolyte-decorated particles ('charge-patch' attraction). The interesting phenomenology shown by these system has a high potential for biotechnological applications, particularly when the primary colloidal particles are bio-compatible lipid vesicles. Possible applications of these systems as multi-compartment vectors for the simultaneous intra-cellular delivery of different pharmacologically active substances will be briefly discussed.

By means of the combined use of dynamic light scattering and transmission electron microscopy measurements, we provide a direct evidence for the existence of an equilibrium cluster phase in the polyion-induced liposome aggregation, where the liposomes maintain their integrity, with the ability of preserving the aqueous core content from the external medium. We prepared single liposomes containing, in their interior, different CsCl electrolyte solutions at different concentrations (0.1 and 0.01 M, respectively). During the polyion-induced complexation of a mixture of these two differently loaded liposomes, reversible aggregates form, whose multicompartmental structure reveals the simultaneous presence of nonfused liposomes. Clusters composed by mesoscopic-sized vesicles and realized by charged lipids coupled to oppositely charged polyions are playing an increasingly important role as model systems in a variety of phenomena in soft matter and for their potential use in biomedical applications as drug delivery systems. Aggregates of liposomes such as those described in this article, where the electrostatic interactions are the primary driving forces promoting aggregation, may represent a new and interesting class of colloids which give rise to a rich phenomenology with several unusual colloidal behaviors that deserve to be further investigated.

We have studied the complexation process taking place in cationic liposomes in the presence of anionic polyelectrolytes, in the polyion concentration range from the dilute to the concentrated regime, by combining dynamic light scattering and transmission electron microscopy techniques. We employed as the cationic lipid a two-chained amphiphile (Dioleoyltrimethylammoniumpropane) and sodium polyacrylate salt as the flexible anionic polyelectrolyte. The results evidence a variety of different structures, mainly depending on the liposome-polyion charge ratio, whose peculiar dynamical and structural features are briefly described. In particular, three different polyion concentration regions are found, within which a monomodal or bimodal distribution of aggregates, with a well-defined time evolution, is present. At low polyion content, close to the isoelectric point, large aggregates are formed, deriving from the collapse of the liposomal bilayers into extended charged surfaces, where adsorbed polyions form a two-dimensional strongly correlated array and organize into a two-dimensional Wigner liquid. At high polyion content, above a critical concentration, the size distributions of the complexes are clearly bimodal and a large-component aggregate, continuously increasing with time, coexists with a population of smaller-size aggregates. At an intermediate polyion concentration, spherical, small-size vesicular structures are reformed, connected in a network by polymer chains. A brief discussion tries to summarize our results into a consistent picture.