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Abstract Intimately connected to the rule of life, chirality remains a long-time fascination in biology, chemistry, physics and materials science. Chiral structures, e.g., nucleic acid and cholesteric phase developed from chiral molecules are common in nature and synthetic soft materials. While it was recently discovered that achiral but bent-core mesogens can also form chiral helices, the assembly of chiral microstructures from achiral polymers has rarely been explored. Here, we reveal chiral emergence from achiral conjugated polymers, in which hierarchical helical structures are developed through a multistep assembly pathway. Upon increasing concentration beyond a threshold volume fraction, dispersed polymer nanofibers form lyotropic liquid crystalline (LC) mesophases with complex, chiral morphologies. Combining imaging, X-ray and spectroscopy techniques with molecular simulations, we demonstrate that this structural evolution arises from torsional polymer molecules which induce multiscale helical assembly, progressing from nano- to micron scale helical structures as the solution concentration increases. This study unveils a previously unknown complex state of matter for conjugated polymers that can pave way to a field of chiral (opto)electronics. We anticipate that hierarchical chiral helical structures can profoundly impact how conjugated polymers interact with light, transport charges, and transduce signals from biomolecular interactions and even give rise to properties unimagined before. 

Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.

 

The importance and widespread need for accurate pH monitoring necessitates the fabrication of new pH sensors with high sensitivity that can be used in a variety of environments. However, typical pH sensors have certain limitations ( e.g. , glass electrodes are fragile and require consistent upkeep, colorimetric pH strips are single use and inaccurate). Herein, we examine the pH-response of multilayers consisting of Ti 3 C 2 T x nanosheets and polycations fabricated using layer-by-layer (LbL) assembly. The MXene sheets themselves are pH-responsive due to their hydroxyl surface groups, and this effect may be amplified with the choice of an appropriate polycation. Specifically, the performance of multilayers assembled with the strong electrolyte poly (diallyldimethylammonium) (PDADMA) or pH-sensitive branched polyethylenimine (BPEI) is compared. As expected, the use of a pH-sensitive constituent leads to a 464% increase in pH sensitivity (116 kΩ pH −1 unit vs. 25 kΩ pH −1 unit) as compared to PDADMA. This is due to the conformational changes that BPEI undergoes with (de)protonation as pH changes. Further comparisons with reduced graphene oxide (rGO), which is far less pH responsive, confirm the unique pH responsivity of MXene nanosheets themselves. The ability to enhance response to particular stimuli by changing the constituent polycation demonstrates promise for future use of MXenes in resistive sensors for a variety of stimuli. 

Ti₃C₂T_xbelongs to the family of MXenes, 2D materials with an attractive combination of functional properties suitable for applications such as batteries, supercapacitors, and strain sensors. However, the fabrication of devices and functional coatings based on Ti₃C₂T_xremains challenging as they are prone to chemical degradation by their oxidation to TiO₂. In this paper, we examine the oxidation of Ti₃C₂T_xin air, liquid, and solid media via conductivity measurements to assess the shelf life of Ti₃C₂T_xMXenes. The oxidation of Ti₃C₂T_xwas observed in all the media used in this study, but it is fastest in liquid media and slowest in solid media (including polymer matrices). We also show that the conventional indicators of MXene oxidation, such as changes in color and colloidal stability, are not always reliable. Finally, we demonstrate the acceleration of oxidation under exposure to UV light.