Supramolecular self-assembly and anisotropic patchiness generate long-range networks in polymer-grafted carbon nanotubes, opening new possibilities using industrially attractive processes.

The currently limited comprehension of hierarchical control over out‐of‐equilibrium (dynamic) self‐assembly processes in nanoscience and nanotechnology has limited the exploitation of multicomponent systems in the design of new nanostructured functional materials. In this study's contribution, molecular building blocks with tailored nanoscale anisotropic supramolecular self‐assembly behavior enable the creation of mesoscale percolation networks of multiwalled carbon nanotubes through collinear interconnections at the microscale. This strategy affords polymeric composites with tunable properties at the macroscale, where the organization mechanism is regulated by dynamic self‐assembly at 4 hierarchical levels of auto‐organization. Such multilevel self‐assembly system reduces up to eightfolds the nanotube concentration required for percolation and enhances conductivity up to 6 orders of magnitude against blanks, thus yielding anisotropically semiconducting and conducting materials. The approach is based on casting‐from‐solution, thus simplifying preparative steps when compared to state‐of‐the‐art electron carrier counterparts such as single‐walled carbon nanotube‐, graphene‐, or indium‐tin‐oxide‐based technologies. Finally, promising material transparency levels can be reached across the visible and near‐infrared regimes for compositions above the percolation threshold, which provides new opportunities beyond the current spectral restrictions in commercial transparent conductors.

In this work, we present the synthesis of a novel Zn-Salphen complex containing an allyl group, which was used as building block in the further preparation of a new family of functional terpolymers. These polymers were obtained through radical co-polymerization with methyl metacrylate (MMA) and n-butyl acrylate (nBuA) in different ratios. The supramolecular recognition behavior of each polymer was evaluated via potentiometric measurements against selected anions in aqueous media. Interestingly, this proof of concept study shows that these systems were selective against only fluoride (F⁻) or both, fluoride and acetate (OAc⁻), by tailoring the relative content of Zn-Salphen monomer, thus making them a promising starting point for modular design of chemical sensors through straightforward synthetic approaches.

We present the synthesis and characterization of organic Salphen compounds containing bromine substituents at the para/ortho‐para positions, in their symmetric and non‐symmetric versions, and describe the X‐ray structure and full characterization for the new unsymmetrical varieties. We report for the first time antiproliferative activity in metal‐free brominated Salphen compounds, by evaluations in four human cancer cell lines, cervix (HeLa), prostate (PC‐3), lung (A549) and colon (LS 180) and one non‐cancerous counterpart (ARPE‐19). We assessed in vitro cell viability against controls using the MTT assay ((3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐2H‐tetrazolium bromide)) and determined the concentration required for 50 % growth inhibition (IC₅₀), together with their selectivity vs. non‐cancerous cells. We found promising results against prostate (9.6 μM) and colon (13.5 μM) adenocarcinoma cells. We also found a tradeoff between selectivity (up to 3‐fold vs. ARPE‐19) and inhibition, depending upon the symmetry and bromine‐substitution of the molecules, showing up to 20‐fold higher selectivity vs. doxorubicin controls.

Polymer-grafted nanomaterials based on carbon allotropes and their derivatives (graphene oxide (GO), etc.) are typically prepared by successive reaction stages that depend upon the initial functionalities in the nanostructure and the polymerization type needed for grafting. However, due to the multiple variables involved in the functionalization steps, it is commonly difficult to predict the properties in the final product and to correlate the material history with its final performance. In this work, we explored the steps needed to graft the carboxylic acid moieties in GO (COOH@GO) with a pH-sensitive polymer, poly[2-(diethylamino)ethyl methacrylate] (poly[DEAEMA]), varying the reactant ratios at each stage prior to polymerization. We studied the combinatorial relationship between these variables and the behavior of the novel grafted material GO-g-poly[DEAEMA], in terms of swelling ratio vs. pH (%Q) in solid specimens and potentiometric response vs. Log[H⁺] in a solid-state sensor format. We first introduced N-hydroxysuccinimide (NHS)-ester moieties at the –COOH groups (GO-g-NHS) by a classical activation with N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide (EDC). Then, we substituted the NHS-ester groups by polymerizable amide-linked acrylic moieties using 2-aminoethyl methacrylate (AEMA) at different ratios to finally introduce the polymer chains via radical polymerization in an excess of DEAEMA monomer. We found correlated trends in swelling pH range, interval of maximum and minimum swelling values, response in potentiometry and potentiometric linear range vs. Log[H⁺] and could establish their relationship with the combinatorial stoichiometries in synthetic stages.