Cavity-enhanced photon indistinguishability at room temperature and telecom wavelengths.

Indistinguishable single photons in the telecom-bandwidth of optical fibers are indispensable for long-distance quantum communication. Solid-state single photon emitters have achieved excellent performance in key benchmarks, however, the demonstration of indistinguishability at room-temperature remains a major challenge. Here, we report room-temperature photon indistinguishability at telecom wavelengths from individual nanotube defects in a fiber-based microcavity operated in the regime of incoherent good cavity-coupling. The efficiency of the coupled system outperforms spectral or temporal filtering, and the photon indistinguishability is increased by more than two orders of magnitude compared to the free-space limit. Our results highlight a promising strategy to attain optimized non-classical light sources.

Quantum Defect Sensitization via Phase-Changing Supercharged Antibody Fragments.

Quantum defects in single-walled carbon nanotubes promote exciton localization, which enables potential applications in biodevices and quantum light sources. However, the effects of local electric fields on the emissive energy states of quantum defects and how they can be controlled are unexplored. Here, we investigate quantum defect sensitization by engineering an intrinsically disordered protein to undergo a phase change at a quantum defect site. We designed a supercharged single-chain antibody fragment (scFv) to enable a full ligand-induced folding transition from an intrinsically disordered state to a compact folded state in the presence of a cytokine. The supercharged scFv was conjugated to a quantum defect to induce a substantial local electric change upon ligand binding. Employing the detection of a proinflammatory biomarker, interleukin-6, as a representative model system, supercharged scFv-coupled quantum defects exhibited robust fluorescence wavelength shifts concomitant with the protein folding transition. Quantum chemical simulations suggest that the quantum defects amplify the optical response to the localization of charges produced upon the antigen-induced folding of the proteins, which is difficult to achieve in unmodified nanotubes. These findings portend new approaches to modulate quantum defect emission for biomarker sensing and protein biophysics and to engineer proteins to modulate binding signal transduction.

Programming sp3 Quantum Defects along Carbon Nanotubes with Halogenated DNA.

Atomic defect color centers in solid-state systems hold immense potential to advance various quantum technologies. However, the fabrication of high-quality, densely packed defects presents a significant challenge. Herein we introduce a DNA-programmable photochemical approach for creating organic color-center quantum defects on semiconducting single-walled carbon nanotubes (SWCNTs). Key to this precision defect chemistry is the strategic substitution of thymine with halogenated uracil in DNA strands that are orderly wrapped around the nanotube. Photochemical activation of the reactive uracil initiates the formation of sp3 defects along the nanotube as deep exciton traps, with a pronounced photoluminescence shift from the nanotube band gap emission (by 191 meV for (6,5)-SWCNTs). Furthermore, by altering the DNA spacers, we achieve systematic control over the defect placements along the nanotube. This method, bridging advanced molecular chemistry with quantum materials science, marks a crucial step in crafting quantum defects for critical applications in quantum information science, imaging, and sensing.

Surfactant-Aided Stabilization of Individual Carbon Nanotubes in Water around the Critical Micelle Concentration.

Surfactants are widely used to disperse single-walled carbon nanotubes (SWCNTs) and other nanomaterials for liquid-phase processing and characterization. Traditional techniques, however, demand high surfactant concentrations, often in the range of 1-2 wt/v% of the solution. Here, we show that optimal dispersion efficiency can be attained at substantially lower surfactant concentrations of approximately 0.08 wt/v%, near the critical micelle concentration. This unexpected observation is achieved by introducing "bare" nanotubes into water containing the anionic surfactant sodium deoxycholate (DOC) through a superacid-surfactant exchange process that eliminates the need for ultrasonication. Among the diverse ionic surfactants and charged biopolymers explored, DOC exhibits the highest dispersion efficiency, outperforming sodium cholate, a structurally similar bile salt surfactant containing just one additional oxygen atom compared to DOC. Employing all-atomistic molecular dynamics simulations, we unravel that the greater stabilization by DOC arises from its higher binding affinity to nanotubes and a substantially larger free energy barrier that resists nanotube rebundling. Further, we find that this barrier is nonelectrostatic in nature and does not obey the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability, underscoring the important role of nonelectrostatic dispersion and hydration interactions at the nanoscale, even in the case of ionic surfactants like DOC. These molecular insights advance our understanding of surfactant chemistry at the bare nanotube limit and suggest low-energy, surfactant-efficient solution processing of SWCNTs and potentially other nanomaterials.

Direct Writing of Aligned Carbon Nanotubes across a Trench.

Aligned and suspended carbon nanotubes can outperform randomly oriented networks in electronic biosensing and thin-film electronics. However, carbon nanotubes tend to bundle and form random networks. Here, we show that carbon nanotubes spontaneously align in an ammonium deoxycholate surfactant gel even under low shear forces, allowing direct writing and printing of nanotubes into electrically conducting wires and aligned thin layers across trenches. To demonstrate its application potential, we directly printed arrays of disposable electrical biosensors, which show femtomolar sensitivity in the detection of DNA and SARS-CoV-2 RNA.

Functional PDMS Elastomers: Bulk Composites, Surface Engineering, and Precision Fabrication.

Polydimethylsiloxane (PDMS)-the simplest and most common silicone compound-exemplifies the central characteristics of its class and has attracted tremendous research attention. The development of PDMS-based materials is a vivid reflection of the modern industry. In recent years, PDMS has stood out as the material of choice for various emerging technologies. The rapid improvement in bulk modification strategies and multifunctional surfaces has enabled a whole new generation of PDMS-based materials and devices, facilitating, and even transforming enormous applications, including flexible electronics, superwetting surfaces, soft actuators, wearable and implantable sensors, biomedicals, and autonomous robotics. This paper reviews the latest advances in the field of PDMS-based functional materials, with a focus on the added functionality and their use as programmable materials for smart devices. Recent breakthroughs regarding instant crosslinking and additive manufacturing are featured, and exciting opportunities for future research are highlighted. This review provides a quick entrance to this rapidly evolving field and will help guide the rational design of next-generation soft materials and devices.

Rational Structural Design of Polymer Pens for Energy-Efficient Photoactuation.

Photoactuated pens have emerged as promising tools for expedient, mask-free, and versatile nanomanufacturing. However, the challenge of effectively controlling individual pens in large arrays for high-throughput patterning has been a significant hurdle. In this study, we introduce novel generations of photoactuated pens and explore the impact of pen architecture on photoactuation efficiency and crosstalk through simulations and experiments. By introducing a thermal insulating layer and incorporating an air ap in the architecture design, we have achieved the separation of pens into independent units. This new design allowed for improved control over the actuation behavior of individual pens, markedly reducing the influence of neighboring pens. The results of our research suggest novel applications of photoactive composite films as advanced actuators across diverse fields, including lithography, adaptive optics, and soft robotics.

Spontaneous sieving of water from ethanol using angstrom-sized nanopores.

Ethanol is widely used as a precursor in products ranging from drugs to cosmetics. However, distillation of ethanol from aqueous solution is energy intensive and expensive. Here, we show that angstrom-sized nanopores with precisely controlled pore sizes can spontaneously remove water from ethanol-water mixtures through molecular sieving at room temperature and pressure. For small-diameter nanotubes, water-filling is observed, but ethanol is completely excluded, as evidenced by time-dependent density functional theory (TD-DFT) calculations and spectroscopy measurements. Potential of mean force calculations were performed to determine how the free energy barriers for water and ethanol-filling of the nanotubes change with increasing pore size. Water/ethanol selectivity ratio reaching as high as 6700 is observed with a (6,4) nanotube, which has a pore size of 0.204 nm. This selectivity vanishes as the pore size increases beyond 0.306 nm. These findings provide insights that may help realize energy efficient molecular sieving of ethanol and water.

Nanosensor-based monitoring of autophagy-associated lysosomal acidification in vivo.

Autophagy is a cellular process with important functions that drive neurodegenerative diseases and cancers. Lysosomal hyperacidification is a hallmark of autophagy. Lysosomal pH is currently measured by fluorescent probes in cell culture, but existing methods do not allow for quantitative, transient or in vivo measurements. In the present study, we developed near-infrared optical nanosensors using organic color centers (covalent sp3 defects on carbon nanotubes) to measure autophagy-mediated endolysosomal hyperacidification in live cells and in vivo. The nanosensors localize to the lysosomes, where the emission band shifts in response to local pH, enabling spatial, dynamic and quantitative mapping of subtle changes in lysosomal pH. Using the sensor, we observed cellular and intratumoral hyperacidification on administration of mTORC1 and V-ATPase modulators, revealing that lysosomal acidification mirrors the dynamics of S6K dephosphorylation and LC3B lipidation while diverging from p62 degradation. This sensor enables the transient and in vivo monitoring of the autophagy-lysosomal pathway.

Fluids and Electrolytes under Confinement in Single-Digit Nanopores.

Confined fluids and electrolyte solutions in nanopores exhibit rich and surprising physics and chemistry that impact the mass transport and energy efficiency in many important natural systems and industrial applications. Existing theories often fail to predict the exotic effects observed in the narrowest of such pores, called single-digit nanopores (SDNs), which have diameters or conduit widths of less than 10 nm, and have only recently become accessible for experimental measurements. What SDNs reveal has been surprising, including a rapidly increasing number of examples such as extraordinarily fast water transport, distorted fluid-phase boundaries, strong ion-correlation and quantum effects, and dielectric anomalies that are not observed in larger pores. Exploiting these effects presents myriad opportunities in both basic and applied research that stand to impact a host of new technologies at the water-energy nexus, from new membranes for precise separations and water purification to new gas permeable materials for water electrolyzers and energy-storage devices. SDNs also present unique opportunities to achieve ultrasensitive and selective chemical sensing at the single-ion and single-molecule limit. In this review article, we summarize the progress on nanofluidics of SDNs, with a focus on the confinement effects that arise in these extremely narrow nanopores. The recent development of precision model systems, transformative experimental tools, and multiscale theories that have played enabling roles in advancing this frontier are reviewed. We also identify new knowledge gaps in our understanding of nanofluidic transport and provide an outlook for the future challenges and opportunities at this rapidly advancing frontier.

Localized Photoactuation of Polymer Pens for Nanolithography.

Localized actuation is an important goal of nanotechnology broadly impacting applications such as programmable materials, soft robotics, and nanolithography. Despite significant recent advances, actuation with high temporal and spatial resolution remains challenging to achieve. Herein, we demonstrate strongly localized photoactuation of polymer pens made of polydimethylsiloxane (PDMS) and surface-functionalized short carbon nanotubes based on a fundamental understanding of the nanocomposite chemistry and device innovations in directing intense light with digital micromirrors to microscale domains. We show that local illumination can drive a small group of pens (3 × 3 over 170 µm × 170 µm) within a massively two-dimensional array to attain an out-of-plane motion by more than 7 µm for active molecular printing. The observed effect marks a striking three-order-of-magnitude improvement over the state of the art and suggests new opportunities for active actuation.

van der Waals SWCNT@BN Heterostructures Synthesized from Solution-Processed Chirality-Pure Single-Wall Carbon Nanotubes.

Single-wall carbon nanotubes in boron nitride (SWCNT@BN) are one-dimensional van der Waals heterostructures that exhibit intriguing physical and chemical properties. As with their carbon nanotube counterparts, these heterostructures can form from different combinations of chiralities, providing rich structures but also posing a significant synthetic challenge to controlling their structure. Enabled by advances in nanotube chirality sorting, clean removal of the surfactant used for solution processing, and a simple method to fabricate free-standing submonolayer films of chirality pure SWCNTs as templates for the BN growth, we show it is possible to directly grow BN on chirality enriched SWCNTs from solution processing to form van der Waals heterostructures. We further report factors affecting the heterostructure formation, including an accelerated growth rate in the presence of H2, and significantly improved crystallization of the grown BN, with the BN thickness controlled down to one single BN layer, through the presence of a Cu foil in the reactor. Transmission electron microscopy and electron energy-loss spectroscopic mapping confirm the synthesis of SWCNT@BN from the solution purified nanotubes. The photoluminescence peaks of both (7,5)- and (8,4)-SWCNT@BN heterostructures are found to redshift (by ∼10 nm) relative to the bare SWCNTs. Raman scattering suggests that the grown BN shells pose a confinement effect on the SWCNT core.

MRI-guided microwave ablation and albumin-bound paclitaxel for lung tumors: Initial experience.

Magnetic resonance-guided microwave ablation (MRI-guided MWA) is a new, minimally invasive ablation method for cancer. This study sought to analyze the clinical value of MRI-guided MWA in non-small cell lung cancer (NSCLC). We compared the precision, efficiency, and clinical efficacy of treatment in patients who underwent MRI-guided MWA or computed tomography (CT)-guided microwave ablation (CT-guided MWA). Propensity score matching was used on the prospective cohort (MRI-MWA group, n = 45) and the retrospective observational cohort (CT-MWA group, n = 305). To evaluate the advantages and efficacy of MRI-guided MWA, data including the accuracy of needle placement, scan duration, ablation time, total operation time, length of hospital stay, progression-free survival (PFS), and overall survival (OS) were collected and compared between the two groups. The mean number of machine scans required to adjust the needle position was 7.62 ± 1.69 (range 4-12) for the MRI-MWA group and 9.64 ± 2.14 (range 5-16) for the CT-MWA group (p < 0.001). The mean time for antenna placement was comparable between the MRI and CT groups (54.41 ± 12.32 min and 53.03 ± 11.29 min, p = 0.607). The microwave ablation time of the two groups was significantly different (7.62 ± 2.65 min and 9.41 ± 2.86 min, p = 0.017), while the overall procedure time was comparable (91.28 ± 16.69 min vs. 93.41 ± 16.03 min, p = 0.568). The overall complication rate in the MRI-MWA group was significantly lower than in the CT-MWA group (12% vs. 51%, p = 0.185). The median time to progression was longer in the MRI-MWA group than in the CT-MWA group (11 months [95% CI 10.24-11.75] vs. 9 months [95% CI 8.00-9.99], p = 0.0003; hazard ratio 0.3690 [95% CI 0.2159-0.6306]). OS was comparable in both groups (MRI group 26.0 months [95% CI 25.022-26.978] vs. CT group 23.0 months [95% CI 18.646-27.354], p = 0.18). This study provides hitherto-undocumented evidence of the clinical effects of MRI-guided MWA on patients with NSCLC and determines the relative safety and efficiency of MRI- and CT-guided MWA.

Can armchair nanotubes host organic color centers?

We use time-dependent density functional theory to investigate the possibility of hosting organic color centers in (6, 6) armchair single-walled carbon nanotubes, which are known to be metallic. Our calculations show that in short segments of (6, 6) nanotubes∼5nm in length there is a dipole-allowed singlet transition related to the quantum confinement of charge carriers in the smaller segments. The introduction ofsp3defects to the surface of (6, 6) nanotubes results in new dipole-allowed excited states. Some of these states are redshifted from the native confinement state of the defect-free (6, 6) segments; this is similar behavior to what is observed withsp3defects to exciton transitions in semiconducting carbon nanotubes. This result suggests the possibility of electrically wiring organic color centers directly through armchair carbon nanotube hosts.

Quantum Coupling of Two Atomic Defects in a Carbon Nanotube Semiconductor.

Chemical defects can create organic color centers in the graphitic lattice of single-walled carbon nanotubes. However, the underlying physics remains somewhat of a mystery. Here we show that two sp3 atomic defects can interact with each other in a way reminiscent of atoms bonding to form molecules. Each defect creates an atom-like mid-gap state within the band gap of the nanotube semiconductor. Two such defects, when brought close to each other, interact to form a split pair of orbitals akin to two hydrogen atoms covalently bonding to form a H2 molecule. This unexpected finding may help in understanding the nature of atomic defects in solids and provide a fresh perspective to the engineering of these color centers.

Engineering defects with DNA.

Single-walled carbon nanotubes are structurally modified by using a genetic sequence.

Quantum Defects: What Pairs with the Aryl Group When Bonding to the sp2 Carbon Lattice of Single-Wall Carbon Nanotubes?

Aryl diazonium reactions are widely used to covalently modify graphitic electrodes and low-dimensional carbon materials, including the recent creation of organic color centers (OCCs) on single-wall carbon nanotube semiconductors. However, due to the experimental difficulties in resolving small functional groups over extensive carbon lattices, a basic question until now remains unanswered: what group, if any, is pairing with the aryl sp3 defect when breaking a C═C bond on the sp2 carbon lattice? Here, we show that water plays an unexpected role in completing the diazonium reaction with carbon nanotubes involving chlorosulfonic acid, acting as a nucleophilic agent that contributes -OH as the pairing group. By simply replacing water with other nucleophilic solvents, we find it is possible to create OCCs that feature an entirely new series of pairing groups, including -OCH3, -OC2H5, -OC3H7, -i-OC3H7, and -NH2, which allows us to systematically tailor the defect pairs and the optical properties of the resulting color centers. Enabled by these pairing groups, we further achieved the synthesis of OCCs with sterically bulky pairs that exhibit high purity defect photoluminescence effectively covering both the second near-infrared window and the telecom wavelengths. Our studies further suggest that these diazonium reactions proceed through the formation of carbocations in chlorosulfonic acid, rather than a radical mechanism that typically occurs in aqueous solutions. These findings uncover the unknown half of the sp3 defect pairs and provide a synthetic approach to control these defect color centers for quantum information, imaging, and sensing.

Parallel Field-Effect Nanosensors Detect Trace Biomarkers Rapidly at Physiological High-Ionic-Strength Conditions.

Sensitivity and speed of detection are contradicting demands that profoundly impact the electrical sensing of molecular biomarkers. Although single-molecule sensitivity can now be achieved with single-nanotube field-effect transistors, these tiny sensors, with a diameter less than 1 nm, may take hours to days to capture the molecular target at trace concentrations. Here, we show that this sensitivity-speed challenge can be addressed using covalently functionalized double-wall CNTs that form many individualized, parallel pathways between two electrodes. Each carrier that travels across the electrodes is forced to take one of these pathways that are fully gated chemically by the target-probe binding events. This sensor design allows us to electrically detect Lyme disease oligonucleotide biomarkers directly at the physiological high-salt concentrations, simultaneously achieving both ultrahigh sensitivity (as low as 1 fM) and detection speed (<15 s). This unexpectedly simple strategy may open opportunities for sensor designs to broadly achieve instant detection of trace biomarkers and real-time probing of biomolecular functions directly at their physiological states.

Formation of organic color centers in air-suspended carbon nanotubes using vapor-phase reaction.

Organic color centers in single-walled carbon nanotubes have demonstrated exceptional ability to generate single photons at room temperature in the telecom range. Combining the color centers with pristine air-suspended nanotubes would be desirable for improved performance, but all current synthetic methods occur in solution which makes them incompatible. Here we demonstrate the formation of color centers in air-suspended nanotubes using a vapor-phase reaction. Functionalization is directly verified by photoluminescence spectroscopy, with unambiguous statistics from more than a few thousand individual nanotubes. The color centers show strong diameter-dependent emission, which can be explained with a model for chemical reactivity considering strain along the tube curvature. We also estimate the defect density by comparing the experiments with simulations based on a one-dimensional exciton diffusion equation. Our results highlight the influence of the nanotube structure on vapor-phase reactivity and emission properties, providing guidelines for the development of high-performance near-infrared quantum light sources.