Plant nanobionics approach to augment photosynthesis and biochemical sensing.

The interface between plant organelles and non-biological nanostructures has the potential to impart organelles with new and enhanced functions. Here, we show that single-walled carbon nanotubes (SWNTs) passively transport and irreversibly localize within the lipid envelope of extracted plant chloroplasts, promote over three times higher photosynthetic activity than that of controls, and enhance maximum electron transport rates. The SWNT-chloroplast assemblies also enable higher rates of leaf electron transport in vivo through a mechanism consistent with augmented photoabsorption. Concentrations of reactive oxygen species inside extracted chloroplasts are significantly suppressed by delivering poly(acrylic acid)-nanoceria or SWNT-nanoceria complexes. Moreover, we show that SWNTs enable near-infrared fluorescence monitoring of nitric oxide both ex vivo and in vivo, thus demonstrating that a plant can be augmented to function as a photonic chemical sensor. Nanobionics engineering of plant function may contribute to the development of biomimetic materials for light-harvesting and biochemical detection with regenerative properties and enhanced efficiency.

Recent advances in molecular recognition based on nanoengineered platforms.

Nanoparticles and nanoengineered platforms have great potential for technologies involving biomoleuclar detection or cell-related biosensing, and have provided effective chemical interfaces for molecular recognition. Typically, chemists work on the modification of synthetic polymers or macromolecules, which they link to the nanoparticles by covalent or noncovalent approaches. The motivation for chemical modification is to enhance the selectivity and sensitivity, and to improve the biocompatibility for the in vivo applications. In this Account, we present recent advances in the development and application of chemical interfaces for molecular recognition for nanoparticles and nanoengineered platforms, in particular single-walled carbon nanotubes (SWNTs). We discuss emerging approaches for recognizing small molecules, glycosylated proteins, and serum biomarkers. For example, we compare and discuss detection methods for ATP, NO, H2O2, and monosaccharides for recent nanomaterials. Fluorometric detection appears to have great potential for quantifying concentration gradients and determining their location in living cells. For macromolecular detection, new methods for glycoprofiling using such interfaces appear promising, and benefit specifically from the potential elimination of cumbersome labeling and liberation steps during conventional analysis of glycans, augmenting the currently used mass spectrometry (MS), capillary electrophoresis (CE), and liquid chromatography (LC) methods. In particular, we demonstrated the great potential of fluorescent SWNTs for glycan-lectin interactions sensing. In this case, SWNTs are noncovalently functionalized to introduce a chelated nickel group. This group provides a docking site for the His-tagged lectin and acts as the signal modulator. As the nickel proximity to the SWNT surface changes, the fluorescent signal is increased or attenuated. When a free glycan or glycosylated probe interacts with the lectin, the signal increases and they are able to obtain loading curves similar to surface plasmon resonance measurements. They demonstrate the sensitivity and specificity of this platform with two higher-affined glycan-lectin pairs: fucose (Fuc) to PA-IIL and N-acetylglucosamine (GlcNAc) to GafD. Lastly, we discuss how developments in protein biomarker detection in general are benefiting specifically from label-free molecular recognition. Electrical field effect transistors, chemi-resistive and fluorometric nanosensors based on various nanomaterials have demonstrated substantial progress in recent years in addressing this challenging problem. In this Account, we compare the balance between sensitivity, selectivity, and nonspecific adsorption for various applications. In particular, our group has utilized SWNTs as fluorescence sensors for label-free protein-protein interaction measurements. In this assay, we have encapsulated each nanotube in a biocompatible polymer, chitosan, which has been further modified to conjugate nitrilotriacetic acid (NTA) groups. After Ni(2+) chelation, NTA Ni(2+) complexes bind to his-tagged proteins, resulting in a local environment change of the SWNT array, leading to optical fluorescence modulation with detection limit down to 100 nM. We have further engineered the platform to monitor single protein binding events, with an even lower detection limit down to 10 pM.

Generating selective saccharide binding affinity of phenyl boronic acids by using single-walled carbon nanotube corona phases.

Saccharides recognition is challenging due to their low affinity for substrates, yet this recognition is critical for human immunity and glycobiology. Herein, we demonstrate that a polymer or surfactant corona phase surrounding a single-walled carbon nanotube can substantially modify the selectivity of pre-adsorbed phenyl-boronic acids (PBA) for mono-, di-, and poly-saccharides. A library of 17 PBAs including carboxy, nitro, and amino PBA with ortho-, meta-, or para- substitutions are used to generate 144 distinct corona phases. Six in particular demonstrate significantly increased selectivity to specific saccharides including ribose (0.42 mol per total mol), arabinose (0.36), and glucose (0.25), but unusually diminished binding to fructose (0.02). Recognition proceeds by saccharide adsorption into the corona, followed by PBA reaction in a consecutive second order reaction. The results extend to larger saccharides, such as glycosaminoglycans, suggesting promise for protein glycosylation.

Charge transfer at junctions of a single layer of graphene and a metallic single walled carbon nanotube.

Junctions between a single walled carbon nanotube (SWNT) and a monolayer of graphene are fabricated and studied for the first time. A single layer graphene (SLG) sheet grown by chemical vapor deposition (CVD) is transferred onto a SiO2/Si wafer with aligned CVD-grown SWNTs. Raman spectroscopy is used to identify metallic-SWNT/SLG junctions, and a method for spectroscopic deconvolution of the overlapping G peaks of the SWNT and the SLG is reported, making use of the polarization dependence of the SWNT. A comparison of the Raman peak positions and intensities of the individual SWNT and graphene to those of the SWNT-graphene junction indicates an electron transfer of 1.12 × 10¹³ cm⁻² from the SWNT to the graphene. This direction of charge transfer is in agreement with the work functions of the SWNT and graphene. The compression of the SWNT by the graphene increases the broadening of the radial breathing mode (RBM) peak from 3.6 ± 0.3 to 4.6 ± 0.5 cm⁻¹ and of the G peak from 13 ± 1 to 18 ± 1 cm⁻¹, in reasonable agreement with molecular dynamics simulations. However, the RBM and G peak position shifts are primarily due to charge transfer with minimal contributions from strain. With this method, the ability to dope graphene with nanometer resolution is demonstrated.

A structure-function relationship for the optical modulation of phenyl boronic acid-grafted, polyethylene glycol-wrapped single-walled carbon nanotubes.

Phenyl boronic acids (PBA) are important binding ligands to pendant diols useful for saccharide recognition. The aromatic ring can also function to anchor an otherwise hydrophilic polymer backbone to the surface of hydrophobic graphene or carbon nanotube. In this work, we demonstrate both functions using a homologous series of seven phenyl boronic acids conjugated to a polyethylene glycol, eight-membered, branched polymer (PPEG8) that allows aqueous dispersion of single-walled carbon nanotubes (SWNT) and quenching of the near-infrared fluorescence in response to saccharide binding. We compare the 2-carboxyphenylboronic acid (2CPBA); 3-carboxy- (3CPBA) and 4-carboxy- (4CPBA) phenylboronic acids; N-(4-phenylboronic)succinamic acid (4SCPBA); 5-bromo-3-carboxy- (5B3CPBA), 3-carboxy-5-fluoro- (5F3CPBA), and 3-carboxy-5-nitro- (5N3CPBA) phenylboronic acids, demonstrating a clear link between SWNT photoluminescence quantum yield and boronic acid structure. Surprisingly, quantum yield decreases systematically with both the location of the BA functionality and the inclusion of electron-withdrawing or -donating substituents on the phenyl ring. For three structural isomers (2CPBA, 3CPBA, and 4CPBA), the highest quantum yields were measured for para-substituted PBA (4CPBA), much higher than ortho- (2CPBA) and meta- (3CPBA) substituted PBA, indicating the first such dependence on molecular structure. Electron-withdrawing substituents such as nitro groups on the phenyl ring cause higher quantum yield, while electron-donating groups such as amides and alkyl groups cause a decrease. The solvatochromic shift of up to 10.3 meV was used for each case to estimate polymer surface coverage on an areal basis using a linear dielectric model. Saccharide recognition using the nIR photoluminescence of SWNT is demonstrated, including selectivity toward pentoses such as arabinose, ribose, and xylose to the exclusion of the expected fructose, which has a high selectivity on PBA due to the formation of a tridentate complex between fructose and PBA. This study is the first to conclusively link molecular structure of an adsorbed phase to SWNT optical properties and modulation in a systematic manner.

Structure and function of glucose binding protein-single walled carbon nanotube complexes.

Understanding the structure and function of glucose binding proteins (GBP) complexed with single walled carbon nanotubes (SWNTs) is important for the development of applications including fluorescent sensors and nanostructure particle tracking. Herein, circular dichroism (CD), thermal denaturation, photo-absorption spectroscopy and atomic force microscopy are used to study these nanostructures. The protein retains its glucose-binding activity after complexation and is thermally stable below 36 °C. However, the SWNT lowers the midpoint denaturation temperature (Tm) by 5 °C and 4 °C in the absence and presence of 10 mM glucose, respectively. This data highlights that using techniques such as CD and thermal denaturation may be necessary to fully characterize such protein-nanomaterial nanostructures.

Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes.

Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes.

NMR methods for characterizing the pore structures and hydrogen storage properties of microporous carbons.

(1)H NMR spectroscopy is used to investigate a series of microporous activated carbons derived from a poly(ether ether ketone) (PEEK) precursor with varying amounts of burnoff (BO). In particular, properties relevant to hydrogen storage are evaluated such as pore structure, average pore size, uptake, and binding energy. High-pressure NMR with in situ H(2) loading is employed with H(2) pressure ranging from 100 Pa to 10 MPa. An N(2)-cooled cryostat allows for NMR isotherm measurements at both room temperature ( approximately 290 K) and 100 K. Two distinct (1)H NMR peaks appear in the spectra which represent the gaseous H(2) in intergranular pores and the H(2) residing in micropores. The chemical shift of the micropore peak is observed to evolve with changing pressure, the magnitude of this effect being correlated to the amount of BO and therefore the structure. This is attributed to the different pressure dependence of the amount of adsorbed and non-adsorbed molecules within micropores, which experience significantly different chemical shifts due to the strong distance dependence of the ring current effect. In pores with a critical diameter of 1.2 nm or less, no pressure dependence is observed because they are not wide enough to host non-adsorbed molecules; this is the case for samples with less than 35% BO. The largest estimated pore size that can contribute to the micropore peak is estimated to be around 2.4 nm. The total H(2) uptake associated with pores of this size or smaller is evaluated via a calibration of the isotherms, with the highest amount being observed at 59% BO. Two binding energies are present in the micropores, with the lower, more dominant one being on the order of 5 kJ mol(-1) and the higher one ranging from 7 to 9 kJ mol(-1).

Density enhancement of aligned single-walled carbon nanotube thin films on quartz substrates by sulfur-assisted synthesis.

The density of the aligned single-walled carbon nanotubes (SWNTs) grown on quartz substrates is an important factor for the performance of fabricated electronic devices. It was discovered that the addition of a sulfur-containing compound (thiophene) to the reaction mixture improved the density of SWNTs by a factor of 2 or more, from approximately 2-4 SWNTs/microm to 6-8 SWNTs/microm under similar growth conditions. It was also observed that along with the increase in nanotube density, the cleanness of the samples improved as well. These effects were demonstrated over a large range of growth conditions, indicating that the addition sulfur makes the growth processes more favorable for the nucleation and growth of aligned SWNTs.

Formation of High-Aspect-Ratio Helical Nanorods via Chiral Self-Assembly of Fullerodendrimers.

Two novel, asymmetric methanofullerenes are presented, which self-assemble in cyclohexane upon thermal cycling to 80 °C. We show that, through the introduction of a dipeptide sequence to one terminus of the dendritic methanofullerene, it is possible to transform the assembly behavior of these molecules from poorly formed aggregates to high-aspect-ratio nanorods. These nanorods have diameters of 3.76 ± 0.52 nm and appear to be composed of interwoven helices of dendritic fullerenes. As evidenced by circular dichroism, the helicity is characterized by a preferential handedness of assembly, which is imparted by the dipeptide moiety.

Single-walled carbon nanotube-based near-infrared optical glucose sensors toward in vivo continuous glucose monitoring.

This article reviews research efforts on developing single-walled carbon nanotube (SWNT)-based near-infrared (NIR) optical glucose sensors toward long-term in vivo continuous glucose monitoring (CGM). We first discuss the unique optical properties of SWNTs and compare SWNTs with traditional organic and nanoparticle fluorophores regarding in vivo glucose-sensing applications. We then present our development of SWNT-based glucose sensors that use glucose-binding proteins and boronic acids as a high-affinity molecular receptor for glucose and transduce binding events on the receptors to modulate SWNT fluorescence. Finally, we discuss opportunities and challenges in translating the emerging technology of SWNT-based NIR optical glucose sensors into in vivo CGM for practical clinical use.

A kinetic model for the deterministic prediction of gel-based single-chirality single-walled carbon nanotube separation.

We propose a kinetic model that describes the separation of single-chirality semiconducting carbon nanotubes based on the chirality-selective adsorption to specific hydrogels. Experimental elution profiles of the (7,3), (6,4), (6,5), (8,3), (8,6), (7,5), and (7,6) species are well described by an irreversible, first-order site association kinetic model with a single rate constant describing the adsorption of each SWNT to the immobile gel phase. Specifically, we find first-order binding rate constants for seven experimentally separated nanotubes normalized by the binding site molarity (M(θ)): k7,3 = 3.5 × 10⁻5 M(θ)⁻¹ s⁻¹, k6,4 = 7.7 × 10⁻8 M(θ)⁻¹ s⁻¹, k8,3 = 2.3 × 10⁻9 M(θ)⁻¹ s⁻¹, k6,5 = 3.8 × 10⁻9 M(θ)⁻¹ s⁻¹, k7,5 = 1.9 × 10⁻¹¹ M(θ)⁻¹ s⁻¹, k8,6 = 7.7 × 10⁻¹² M(θ)⁻¹ s⁻¹, and k7,6 = 3.8 × 10⁻¹² M(θ)⁻¹ s⁻¹. These results, as well as additional control experiments, unambiguously identify the separation process as a selective adsorption. Unlike certain chromatographic processes with retention time dependence, this separation procedure can be scaled to arbitrarily large volumes, as we demonstrate. This study provides a foundation for both the mechanistic understanding of gel-based SWNT separation as well as the potential industrial-scale realization of single-chirality production of carbon nanotubes.

In vivo biosensing via tissue-localizable near-infrared-fluorescent single-walled carbon nanotubes.

Single-walled carbon nanotubes are particularly attractive for biomedical applications, because they exhibit a fluorescent signal in a spectral region where there is minimal interference from biological media. Although single-walled carbon nanotubes have been used as highly sensitive detectors for various compounds, their use as in vivo biomarkers requires the simultaneous optimization of various parameters, including biocompatibility, molecular recognition, high fluorescence quantum efficiency and signal transduction. Here we show that a polyethylene glycol ligated copolymer stabilizes near-infrared-fluorescent single-walled carbon nanotubes sensors in solution, enabling intravenous injection into mice and the selective detection of local nitric oxide concentration with a detection limit of 1 µM. The half-life for liver retention is 4 h, with sensors clearing the lungs within 2 h after injection, thus avoiding a dominant route of in vivo nanotoxicology. After localization within the liver, it is possible to follow the transient inflammation using nitric oxide as a marker and signalling molecule. To this end, we also report a spatial-spectral imaging algorithm to deconvolute fluorescence intensity and spatial information from measurements. Finally, we demonstrate that alginate-encapsulated single-walled carbon nanotubes can function as implantable inflammation sensors for nitric oxide detection, with no intrinsic immune reactivity or other adverse response for more than 400 days.

Polymer-free near-infrared photovoltaics with single chirality (6,5) semiconducting carbon nanotube active layers.

We demonstrate a polymer-free carbon-based photovoltaic device that relies on exciton dissociation at the SWNT/C(60) interface, as shown in the figure. Through the construction of a carbon-based photovoltaic completely free of polymeric active or transport layers, we show both the feasibility of this novel device as well as inform the mechanisms for inefficiencies in SWNTs and carbon based solar cells.

Boronic acid library for selective, reversible near-infrared fluorescence quenching of surfactant suspended single-walled carbon nanotubes in response to glucose.

We describe the high-throughput screening of a library of 30 boronic acid derivatives to form complexes with sodium cholate suspended single-walled carbon nanotubes (SWNTs) to screen for their ability to reversibly report glucose binding via a change in SWNT fluorescence. The screening identifies 4-cyanophenylboronic acid which uniquely causes a reversible wavelength red shift in SWNT emission. The results also identify 4-chlorophenylboronic acid which demonstrates a turn-on fluorescence response when complexed with SWNTs upon glucose binding in the physiological range of glucose concentration. The mechanism of fluorescence modulation in both of these cases is revealed to be a photoinduced excited-state electron transfer that can be disrupted by boronate ion formation upon glucose binding. The results allow for the elucidation of design rules for such sensors, as we find that glucose recognition and transduction is enabled by para-substituted, electron-withdrawing phenyl boronic acids that are sufficiently hydrophobic to adsorb to the nanotube surface.

Sensitive Detection of Elemental Mercury Vapor by Gold Nanoparticle Decorated Carbon Nanotube Sensors.

Low-cost, low power consumption gas sensors that can detect or quantify various gas analytes are of increasing interest for various applications ranging from mobile health, to environmental exposure assessment and homeland security. In particular miniature gas sensors based on nanomaterials that can be manufactured in the form of sensor arrays present great potential for the development of portable monitoring devices. In this study, we demonstrate that a chemiresistive nanosensor comprised of single walled carbon nanotubes decorated with gold nanoparticles has impressive sensitivity to elemental mercury (Hg) gas concentrations, with a lower detection limit as low as 2 ppb(v). Furthermore, this nanosensor was found to regenerate, though slowly, without any additional recovery steps. Finally, the mercury vapor sensing mechanism allowed for direct investigations into the origin of Surface Enhanced Raman Scattering (SERS) in carbon nanotubes decorated with Au nanoparticles.

Viscous state effect on the activity of Fe nanocatalysts.

Many applications of nanotubes and nanowires require controlled bottom-up engineering of these nanostructures. In catalytic chemical vapor deposition, the thermo-kinetic state of the nanocatalysts near the melting point is one of the factors ruling the morphology of the grown structures. We present theoretical and experimental evidence of a viscous state for nanoparticles near their melting point. The state exists over a temperature range scaling inversely with the catalyst size, resulting in enhanced self-diffusion and fluidity across the solid-liquid transformation. The overall effect of this phenomenon on the growth of nanotubes is that, for a given temperature, smaller nanoparticles have a larger reaction rate than larger catalysts.

Selective growth of well-aligned semiconducting single-walled carbon nanotubes.

High-density arrays of perfectly aligned single-walled carbon nanotubes (SWNTs) consisting almost exclusively of semiconducting nanotubes were grown on ST-cut single crystal quartz substrates. Raman spectroscopy together with electrical measurements of field effect transistors (FETs) fabricated from the as-grown samples showed that over 95% of the nanotubes in the arrays are semiconducting. The mechanism of selective growth was explored. It is proposed that introducing methanol in the growth process, combined with the interaction between the SWNTs and the quartz lattice, leads to the selective growth of aligned semiconducting nanotubes. Such a high density of horizontally aligned semiconducting SWNTs can be readily used in high current nanoFETs and sensors. This method demonstrates great promise to solve one of the most difficult problems which limits application of carbon nanotubes in nanoelectronicsthe coexistence of metallic and semiconducting nanotubes in samples produced by most, if not all, growth methods.

Horizontally aligned single-walled carbon nanotube on quartz from a large variety of metal catalysts.

Horizontally aligned single-walled carbon nanotubes (SWNTs) are highly desired for SWNT device applications. A large variety of metals including Fe, Co, Ni, Cu, Pt, Pd, Mn, Mo, Cr, Sn, Au, Mg, and Al successfully catalyzed the growth of such tubes on stable temperature (ST)-cut quartz by lattice guidance. In addition, Mg and Al were presented to produce random and aligned SWNTs for the first time. A hypothesis is proposed in which the precipitated carbon shell on the outer surface of the metal catalysts guides the alignment along the crystal lattice but not the catalysts themselves. By elucidating the role of the catalysts, an understanding of the aligned growth mechanism on quartz is further improved. Moreover, a simple "scratch" method by a razor blade such as the carbon steel and tungsten carbide (with 9% cobalt) is presented to pattern the "catalysts" without any complex processing steps such as lithography for the aligned SWNT growth.