The optical transition energies (Eii) of single-walled carbon nanotubes (SWCNT) are influenced by the local environment created by solvents and adsorbed molecules. Analysis of SWCNT photoluminescence (PL) energies in various dielectric media is used to elucidate a semiempirical scaling relation for Eii shifts and nanotube structural properties from a classical solvatochromic formalism. The SWCNT Kataura plot is corrected for a dielectric constant of unity and used in conjunction with the scaling to accurately describe PL energy shifts in a broad range of dielectric media.

Intracellular protein motors have evolved to perform specific tasks critical to the function of cells such as intracellular trafficking and cell division. Kinesin and dynein motors, for example, transport cargoes in living cells by walking along microtubules powered by adenosine triphosphate hydrolysis. These motors can make discrete 8 nm centre-of-mass steps and can travel over 1 µm by changing their conformations during the course of adenosine triphosphate binding, hydrolysis and product release. Inspired by such biological machines, synthetic analogues have been developed including self-assembled DNA walkers that can make stepwise movements on RNA/DNA substrates or can function as programmable assembly lines. Here, we show that motors based on RNA-cleaving DNA enzymes can transport nanoparticle cargoes-CdS nanocrystals in this case-along single-walled carbon nanotubes. Our motors extract chemical energy from RNA molecules decorated on the nanotubes and use that energy to fuel autonomous, processive walking through a series of conformational changes along the one-dimensional track. The walking is controllable and adapts to changes in the local environment, which allows us to remotely direct 'go' and 'stop' actions. The translocation of individual motors can be visualized in real time using the visible fluorescence of the cargo nanoparticle and the near-infared emission of the carbon-nanotube track. We observed unidirectional movements of the molecular motors over 3 µm with a translocation velocity on the order of 1 nm min(-1) under our experimental conditions.

Magnetic iron oxide nanoparticles and near-infrared (NIR) fluorescent single-walled carbon nanotubes (SWNT) form heterostructured complexes that can be utilized as multimodal bioimaging agents. Fe catalyst-grown SWNT were individually dispersed in aqueous solution via encapsulation by oligonucleotides with the sequence d(GT) 15 , and enriched using a 0.5 T magnetic array. The resulting nanotube complexes show distinct NIR fluorescence, Raman scattering, and visible/NIR absorbance features, corresponding to the various nanotube species. AFM and cryo-TEM images show DNA-encapsulated complexes composed of a ∼3 nm particle attached to a carbon nanotube on one end. X-ray diffraction (XRD) and superconducting quantum interference device (SQUID) measurements reveal that the nanoparticles are primarily Fe 2 O 3 and superparamagnetic. The Fe 2 O 3 particle-enriched nanotube solution has a magnetic particle content of ∼35 wt %, a magnetization saturation of ∼56 emu/g, and a magnetic relaxation time scale ratio (T 1 /T 2 ) of approximately 12. These complexes have a longer spin−spin relaxation time (T 2 ∼ 164 ms) than typical ferromagnetic particles due to the smaller size of their magnetic component while still retaining SWNT optical signatures. Macrophage cells that engulf the DNA-wrapped complexes were imaged using magnetic resonance imaging (MRI) and NIR mapping, demonstrating that these multifunctional nanostructures could potentially be useful in multimodal biomedical imaging.

Atomically thin transition metal dichalcogenides (TMDCs) have attracted great interest as a new class of two-dimensional (2D) direct band gap semiconducting materials. The controllable modulation of optical and electrical properties of TMDCs is of fundamental importance to enable a wide range of future optoelectronic devices. Here we demonstrate a modulation of the optoelectronic properties of 2D TMDCs, including MoS2, MoSe2, and WSe2, by interfacing them with two metal-centered phthalocyanine (MPc) molecules: nickel Pc (NiPc) and magnesium Pc (MgPc). We show that the photoluminescence (PL) emission can be selectively and reversibly engineered through energetically favorable electron transfer from photoexcited TMDCs to MPcs. NiPc molecules, whose reduction potential is positioned below the conduction band minima (CBM) of monolayer MoSe2 and WSe2, but is higher than that of MoS2, quench the PL signatures of MoSe2 and WSe2, but not MoS2. Similarly, MgPc quenches only WSe2, as its reduction potential is situated below the CBM of WSe2, but above those of MoS2 and MoSe2. The quenched PL emission can be fully recovered when MPc molecules are removed from the TMDC surfaces, which may be refunctionalized and recycled multiple times. We also find that photocurrents from TMDCs, probed by photoconductive atomic force microscopy, increase over 2-fold only when the PL is quenched by MPcs, further supporting the photoinduced charge transfer mechanism. Our results should benefit design strategies for 2D inorganic-organic optoelectronic devices and systems with tunable properties and improved performances.

We demonstrate that aptamer-capped near-infrared PbS quantum dots (QDs) can detect a target protein based on selective charge transfer. The water-soluble QDs are synthesized with the thrombin-binding aptamer, which retains the secondary quadruplex structure necessary for binding to thrombin. These QDs have diameters of 3-6 nm and fluoresce around 1050 nm. When the aptamer-functionalized QD binds to its target, a fluorescence quenching occurs due to charge transfer from amine groups on the protein to the QD. Thrombin is detected within 1 min with a detection limit of approximately 1 nM. This selective detection is observed even in the presence of high background concentrations of interfering negatively or positively charged proteins, suggesting that aptamer-capped QDs could be useful for label-free protein assays.

The unique physical properties of single-wall carbon nanotubes (SWCNTs) have been exploited in novel applications in various fields including electronics and life sciences. Their photoluminescence in the near-infrared (NIR) range, where optical interference from biological tissues is minimum, has rendered them particularly attractive as optical probes in biological environments. Herein we review the use of the SWCNT NIR emission in bio-sensing and imaging.To interface the insoluble carbon nanotubes with aqueous biological environment, biomaterials and organic polymers have been widely used for non-covalently functionalizing SWCNTs. Such functionalization minimizes the toxicity of carbon nanotubes in biological and physiological environments, while maintaining its optical properties. SWCNTs have been demonstrated as both in vitro and in vivo optical sensors, targeting biologically important molecules, such as neurotransmitters and cell signaling molecules. For optical imaging, functionalized SWCNTs were used as NIR contrast agents for probing cellular processes and imaging plants and small animals.We also discuss emerging SWCNT-based super-resolution schemes. We conclude that SWCNTs are promising optical materials for basic life science research, biomedical diagnostics, and therapeutics.

We report a novel optical biosensor platform using near-infrared (NIR) fluorescent single-walled carbon nanotubes (SWNTs) functionalized with target-recognizing aptamer DNA for noninvasively detecting cell signaling molecules in real-time. Photoluminescence (PL) emission of aptamer-coated SWNTs is modulated upon selectively binding to target molecules, which is exploited to detect insulin using an insulin-binding aptamer (IBA) as a molecular recognition element. We find that nanotube PL quenches upon insulin recognition via a photoinduced charge transfer mechanism with a quenching rate of kq = 5.85×1014 M−1s−1 and a diffusion-reaction rate of kr = 0.129 s−1. Circular dichroism spectra reveal for the first time that IBA strands retain a four-stranded, parallel guanine quadruplex conformation on the nanotubes, ensuring target selectivity. We demonstrate that these IBA-functionalized SWNT sensors incorporated in a collagen extracellular matrix (ECM) can be regenerated by removing bound analytes through enzymatic proteolysis. As proof-of-concept, we show that the SWNT sensors embedded in the ECM promptly detect insulin secreted by cultured pancreatic INS-1 cells stimulated by glucose influx and report a gradient contour of insulin secretion profile. This novel design enables new types of label-free assays and non-invasive, in-situ, real-time detection schemes for cell signaling molecules.

Naturally occurring photosynthetic systems use elaborate pathways of self-repair to limit the impact of photo-damage. Herein, we demonstrate a complex that mimics this process consisting of two recombinant proteins, phospholipids and a carbon nanotube. The components self-assemble into a configuration in which an array of lipid bilayers aggregate on the surface of the carbon nanotube, creating a platform for the attachment of light-converting proteins. The system can disassemble upon the addition of a surfactant and reassemble on its removal over an indefinite number of cycles. The assembly is thermodynamically meta-stable and can only transition reversibly if the rate of surfactant removal exceeds about 10−5 sec−1. Only in the assembled state do the complexes exhibit photoelectrochemical activity. We demonstrate a regeneration cycle that uses surfactant to switch between assembled and disassembled states, resulting in increased photo-conversion efficiency of more than 300% over 168 hours and an indefinite extension of the system's lifetime.