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Realization of topological quantum states in carbon nanostructures has recently emerged as a promising platform for hosting highly coherent and controllable quantum dot spin qubits. However, their adjustable manipulation remains elusive. Here, we report the atomically accurate control of the hybridization level of topologically protected quantum edge states emerging from topological interfaces in bottom-up-fabricated π-conjugated polymers. Our investigation employed a combination of low-temperature scanning tunneling microscopy and spectroscopy, along with high-resolution atomic force microscopy, to effectively modify the hybridization level of neighboring edge states by the selective dehydrogenation reaction of molecular units in a pentacene-based polymer and demonstrate their reversible character. Density functional theory, tight binding, and complete active space calculations for the Hubbard model were employed to support our findings, revealing that the extent of orbital overlap between the topological edge states can be finely tuned based on the geometry and electronic bandgap of the interconnecting region. These results demonstrate the utility of topological edge states as components for designing complex quantum arrangements for advanced electronic devices.

Precise control of multiple spin states on the atomic scale presents a promising avenue for designing and realizing magnetic switches. Despite substantial progress in recent decades, the challenge of achieving control over multiconfigurational reversible switches in low-dimensional nanostructures persists. Our work demonstrates multiple, fully reversible plasmon-driven spin-crossover switches in a single π-d metal-organic chain suspended between two electrodes. The plasmonic nanocavity stimulated by external visible light allows for reversible spin crossover between low- and high-spin states of different cobalt centers within the chain. We show that the distinct spin configurations remain stable for minutes under cryogenic conditions and can be nonperturbatively detected by conductance measurements. This multiconfigurational plasmon-driven spin-crossover demonstration extends the available toolset for designing optoelectrical molecular devices based on SCO compounds.

Microsupercapacitors (micro-SCs) with mechanical flexibility have the potential to complement or even replace microbatteries in the portable electronics sector, particularly for portable biomonitoring devices. The real-time biomonitoring of the human body's physical status using lightweight, flexible, and wearable micro-SCs is important to consider, but the main limitation is, however, the low energy density of micro-SCs as compared to microbatteries. Here using a temporally and spatially controlled picosecond pulsed laser, we developed high-energy-density micro-SCs integrated with a force sensing device to monitor a human body's radial artery pulses. The photochemically synthesized spherical laser-induced MXene (Ti 3 C 2 T x )-derived oxide nanoparticles uniformly attached to laser-induced graphene (LIG) act as active electrode materials for micro-SCs. The molecular dynamics simulations and detailed spectroscopic analysis reveal the synergistic interfacial interaction mechanism of Ti-O-C covalent bonding between MXene and LIG. The incorporation of MXene nanosheets improves the graphene sheet alignment and ion transport while minimizing self-restacking. Furthermore, the micro-SCs based on a nano-MXene-LIG hybrid demonstrate high mechanical flexibility, durability, ultrahigh energy density (21.16 × 10 -3 mWh cm -2 ), and excellent capacitance (∼100 mF cm -2 @ 10 mV s -1 ) with long cycle life (91% retention after 10 000 cycles). Such a single-step roll-to-roll highly reproducible manufacturing technique using a picosecond pulsed laser to induce MXene-derived spherical oxide nanoparticles (size of quantum dots) attached uniformly to laser-induced graphene for biomedical device fabrication is expected to find a wide range of applications.

Nanoscale investigation of the reactivity of photocatalytic systems is crucial for their fundamental understanding and improving their design and applicability. Here, we present a photochemical nanoscopy technique that unlocks the local spatial detection of molecular products during plasmonic hot-carrier-driven photocatalytic reactions with nanometric precision. By applying the methodology to Au/TiO 2 plasmonic photocatalysts, we experimentally and theoretically determined that smaller and denser Au nanoparticle arrays present lower optical contribution with quantum efficiency in hot-hole-driven photocatalysis closely related to the population heterogeneity. As expected, the highest quantum yield from a redox probe oxidation is achieved at the plasmon peak. Investigating a single plasmonic nanodiode, we unravel the areas where oxidation and reduction products are evolved with subwavelength resolution (∼200 nm), illustrating the bipolar behavior of such nanosystems. These results open the way to quantitative investigations at the nanoscale to evaluate the photocatalytic reactivity of low-dimensional materials in a variety of chemical reactions.

Improving the effectiveness of cancer therapy will require tools that enable more specific cancer targeting and improved tumor visualization. Theranostics have the potential for improving cancer care because of their ability to serve as both diagnostics and therapeutics; however, their diagnostic potential is often limited by tissue-associated light absorption and scattering. Herein, we develop CuInSe 2 @ZnS:Mn quantum dots (QDs) with intrinsic multifunctionality that both enable the accurate localization of small metastases and act as potent tumor ablation agents. By leveraging the growth kinetics of a ZnS shell on a biocompatible CuInSe 2 core, Mn doping, and folic acid functionalization, we produce biocompatible QDs with high near-infrared (NIR)-II fluorescence efficiency up to 31.2%, high contrast on magnetic resonance imaging (MRI), and preferential distribution in 4T1 breast cancer tumors. MRI-enabled contrast of these nanoprobes is sufficient to timely identify small metastases in the lungs, which is critically important for preventing cancer spreading and recurrence. Further, exciting tumor-resident QDs with NIR light produces both fluorescence for tumor visualization through radiative recombination pathways as well as heat and radicals through nonradiative recombination pathways that kill cancer cells and initiate an anticancer immune response, which eliminates tumor and prevents tumor regrowth in 80% of mice.

Rapid progress on developing smart materials and design of hybrids is motivated by pressing challenges associated with energy crisis and environmental remediation. While emergence of versatile classes of nanomaterials has been fascinating, the real excitement lies in the design of hybrid materials with tunable properties. Metal-organic frameworks (MOFs) are the key materials for gas sorption and electrochemical applications, but their sustainability is challenged by limited chemical stability, poor electrical conductivity, and intricate, inaccessible pores. Despite tremendous efforts towards improving the stability of MOF materials, little progress has made researchers inclined toward developing hybrid materials. MXenes, a family of two-dimensional transition-metal carbides, nitrides and carbonitrides, are known for their compositional versatility and formation of a range of structures with rich surface chemistry. Hybridization of MOFs with functional layered MXene materials may be beneficial if the host structure provides appropriate interactions for stabilizing and improving the desired properties. Recent efforts have focused on integrating Ti 3 C 2 T x and V 2 CT x MXenes with MOFs to result in hybrid materials with augmented electrochemical and physicochemical properties, widening the scope for emerging applications. This review discusses the potential design strategies of MXene@MOF hybrids, attributes of tunable properties in the resulting hybrids, and their applications in water treatment, sensing, electrochemical energy storage, smart textiles, and electrocatalysis. Comprehensive discussions on the recent efforts on rapidly evolving MXene@MOF materials for various applications and potential future directions are highlighted.

The conversion of nitrogen to ammonia offers a sustainable and environmentally friendly approach for producing precursors for fertilizers and efficient energy carriers. Owing to the large energy density and significant gravimetric hydrogen content, NH 3 is considered an apt next-generation energy carrier and liquid fuel. However, the low conversion efficiency and slow production of ammonia through the nitrogen reduction reaction (NRR) are currently bottlenecks, making it an unviable alternative to the traditional Haber-Bosch process for ammonia production. The rational design and engineering of catalysts (both photo- and electro-) represent a crucial challenge for improving the efficiency and exploiting the full capability of the NRR. In the present review, we highlight recent progress in the development of graphene-based systems and graphene derivatives as catalysts for the NRR. Initially, the history, fundamental mechanism, and importance of the NRR to produce ammonia are briefly discussed. We also outline how surface functionalization, defects, and hybrid structures (single-atom/multiatom as well as composites) affect the N 2 conversion efficiency. The potential of graphene and graphene derivatives as NRR catalysts is highlighted using pertinent examples from theoretical simulations as well as machine learning based performance predictive methods. The review is concluded by identifying the crucial advantages, drawbacks, and challenges associated with principal scientific and technological breakthroughs in ambient catalytic NRR.

The design and fabrication of active nanomaterials exhibiting multifunctional properties is a must in the so-called global "Fourth Industrial Revolution". In this sense, molecular engineering is a powerful tool to implant original capabilities on a macroscopic scale. Herein, different bioinspired 2D-MXenes have been developed via a versatile and straightforward synthetic approach. As a proof of concept, Ti 3 C 2 T x MXene has been exploited as a highly sensitive transducing platform for the covalent assembly of active biomolecular architectures ( i.e. , amino acids). All pivotal properties originated from the anchored targets were proved to be successfully transferred to the resulting bioinspired 2D-MXenes. Appealing applications have been devised for these 2D-MXene prototypes showing (i) chiroptical activity, (ii) fluorescence capabilities, (iii) supramolecular π-π interactions, and (iv) stimuli-responsive molecular switchability. Overall, this work demonstrates the fabrication of programmable 2D-MXenes, taking advantage of the inherent characteristics of the implanted (bio)molecular components. Thus, the current bottleneck in the field of 2D-MXenes can be overcome after the significant findings reported here.

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Reducing the size of a catalyst to a single atom (SA) level can dramatically change its physicochemical properties and significantly boost its catalytic activity. However, the massive synthesis of SA catalysts still remains a grand challenge mainly because of the aggregation and nucleation of the generated atoms during the reaction. Here, we design and implement a spatially confined synthetic strategy based on a porous-hollow carbon nitride ( p -CN) coordinated with 1-butyl-3-methylimidazole hexafluorophosphate, which can act as a nanoreactor and allow us to obtain metal SA catalysts ( p -CN@M SAs). This relatively easy and highly effective method provides a way to massively synthesize single/multiple atoms ( p -CN@M SAs, M = Pt, Pd, Cu, Fe, etc .). Moreover, the amorphous NiB-coated p -CN@Pt SAs can further increase the loading amount of Pt SAs to 3.7 wt %. The synthesized p -CN@Pt&NiB electrocatalyst exhibits an extraordinary hydrogen evolution reaction activity with the overpotential of 40.6 mV@10 mA/cm -2 and the Tofel slope of 29.26 mV/dec.

Sorption technologies, enabling removal of heavy metals, play a pivotal role in meeting the global demands for unrestricted access to drinking water. Standard sorption technologies suffer from limited efficiency related to the weak sorbent-metal interaction. Further challenges include the development of technologies enabling smart metal recovery and sorbent regeneration. To this end, a densely functionalized graphene, with 33% by mass content of carboxyl groups, linked through direct C-C bonds (graphene acid, GA) represents a previously unexplored solution to this challenge. GA revealed excellent efficiency for removal of highly toxic metals, such as Cd 2+ and Pb 2+ . Due to its selective chemistry, GA can bind heavy metals with high affinity, even at concentrations of 1 mg L -1 and in the presence of competing ions of natural drinking water, and reduce them down to drinking water allowance levels of a few μg L -1 . This is not only due to carboxyl groups but also due to the stable radical centers of the GA structure, enabling metal ion-radical interactions, as proved by EPR, XPS, and density functional theory calculations. GA offers full structural integrity during the highly acidic and basic treatment, which is exploited for noble metal recovery (Ga 3+ , In 3+ , Pd 2+ ) and sorbent regeneration. Owing to these attributes, GA represents a fully reusable metal sorbent, applicable also in electrochemical energy technologies, as illustrated with a GA/Pt catalyst derived from Pt 4+ -contaminated water.