Carbon dots have attracted widespread interest for sensing applications based on their low cost, ease of synthesis, and robust optical properties. We investigate structure-function evolution on multiemitter fluorescence patterns for model carbon-nitride dots (CNDs) and their implications on trace-level sensing. Hydrothermally synthesized CNDs with different reaction times were used to determine how specific functionalities and their corresponding fluorescence signatures respond upon the addition of trace-level analytes. Archetype explosives molecules were chosen as a testbed due to similarities in substituent groups or inductive properties (i.e., electron withdrawing), and solution-based assays were performed using ratiometric fluorescence excitation-emission mapping (EEM). Analyte-specific quenching and enhancement responses were observed in EEM landscapes that varied with the CND reaction time. We then used self-organizing map models to examine EEM feature clustering with specific analytes. The results reveal that interactions between carbon-nitride frameworks and molecular-like species dictate response characteristics that may be harnessed to tailor sensor development for specific applications.
We report a spontaneous and hierarchical self-assembly mechanism of carbon dots prepared from citric acid and urea into nanowire structures with large aspect ratios (>50). Scattering-type scanning near-field optical microscopy (s-SNOM) with broadly tunable mid-IR excitation was used to interrogate details of the self-assembly process by generating nanoscopic chemical maps of local wire morphology and composition. s-SNOM images capture the evolution of wire formation and the complex interplay between different chemical constituents directing assembly over the nano- to microscopic length scales. We propose that residual citrate promotes tautomerization of melamine surface functionalities to produce supramolecular shape synthons comprised of melamine-cyanurate adducts capable of forming long-range and highly directional hydrogen-bonding networks. This intrinsic, heterogeneity-driven self-assembly mechanism reflects synergistic combinations of high chemical specificity and long-range cooperativity that may be harnessed to reproducibly fabricate functional structures on arbitrary surfaces.
The effective management of plastic waste streams to prevent plastic land and water pollution is a growing problem that is also one of the most important challenges in polymer science today. Polymer materials that are stable over their lifetime and can also be cheaply recycled or repurposed as desired could more easily be diverted from waste streams. However, this is difficult for most commodity plastics. It is especially difficult to conceive this with intractable, cross-linked polymers such as rubbers. In this work, we explore the utility of microencapsulated Grubbs’ catalysts for the in-situ depolymerization and reprocessing of polybutadiene (PB) rubber. Second-generation Hoveyda-Grubbs catalyst (HG2) contained within glassy thermoplastic microspheres can be dispersed in PB rubber below the microsphere’s glass transition temperature (Tg) without adverse depolymerization, evidenced by rubber with and without these microspheres obtaining similar shear storage moduli of ≈16 and ≈28 kPa, respectively. The thermoplastic’s Tg can be used to tune the depolymerization temperature, via release of HG2 into the rubber matrix. For example, using poly(lactic acid) (PLA) vs polysulfone results in an 85 and 162 °C depolymerization temperature, respectively. Liquefaction of rubber to a mixture of small molecules and oligomers is demonstrated using a 0.01 mol % catalyst loading using PLA as the encapsulant. At that same catalyst loading, depolymerization occurs to a greater extent in comparison to two ex-situ approaches, including a conventional solvent-assisted method, where it occurs at roughly twice the extent at each given catalyst loading. In addition, depolymerization of the microsphere-loaded rubbers was demonstrated for samples stored under nitrogen for 23 days. Lastly, we show that the depolymerized products can be reprocessed back into solid rubber with a shear storage modulus of ≈32 kPa. Thus, we envision that this approach could be used to recycle and reuse cross-linked rubbers at the end of their product lifetime.
Plastics, with their ubiquitous presence in our daily lives and environment, pose an uncomfortable conundrum. Producers and consumers are aware of the value of these organic ingredients in material flow, yet their persistence and disruption to the ecological milieu desperately stipulate a shift in the status quo. Biodegradable plastics-as the name suggests-has its appeal in ensuring the safe return of carbon to ecosystems by complete assimilation of the degraded product as a food source for soil or aquatic microorganisms. However, despite more than a decade of commercial presence, these plastics are still far from replacing the demand for fossil-fuel-based commodity plastics. We discuss this apparent disconnect herein through a material value chain perspective. We review the current state of commercial biodegradable plastics and contrast it against the desired state of the zero-waste-focused circular economy. To close the gap, we suggest critical research needs concerning the structure and properties of biodegradable plastics, testing standards, application development, and waste management. The ultimate success in displacing conventional plastics with biodegradable alternatives will be predicated on collaboration between all stakeholders across the product value chain.
