Polarized X-ray scattering measures molecular orientation in polymer-grafted nanoparticles.

Polymer chains are attached to nanoparticle surfaces for many purposes, including altering solubility, influencing aggregation, dispersion, and even tailoring immune responses in drug delivery. The most unique structural motif of polymer-grafted nanoparticles (PGNs) is the high-density region in the corona where polymer chains are stretched under significant confinement, but orientation of these chains has never been measured because conventional nanoscale-resolved measurements lack sensitivity to polymer orientation in amorphous regions. Here, we directly measure local chain orientation in polystyrene grafted gold nanoparticles using polarized resonant soft X-ray scattering (P-RSoXS). Using a computational scattering pattern simulation approach, we measure the thickness of the anisotropic region of the corona and extent of chain orientation within it. These results demonstrate the power of P-RSoXS to discover and quantify orientational aspects of structure in amorphous soft materials and provide a framework for applying this emerging technique to more complex, chemically heterogeneous systems in the future.

Tuning Hierarchical Order and Plasmonic Coupling of Large-Area, Polymer-Grafted Gold Nanorod Assemblies via Flow-Coating.

Solution-based printing of anisotropic nanostructures is foundational to many emerging technologies, such as energy storage devices, photonic elements, and sensors. Methods to rapidly (>mm/s) manufacture large area assemblies (≫cm2) with simultaneous control of thickness (<10 nm), nanoparticle spacing (<5 nm), surface roughness (<5 nm), and global and local orientational order are still lacking. Herein, we demonstrate such capability using flow-coating to fabricate robust, self-supporting mono- and bilayer films of polystyrene-grafted gold nanorods (PS-AuNRs) onto solid substrates. The relationship among solvent evaporation, deposition speed, substrate surface energy, concentration, and film thickness for solutions of such hairy hybrid nanoparticles spans the Landau-Levich and evaporative film formation regimes. In the Landau-Levich regime, solvent evaporation rapidly concentrates the PS-AuNRs, leading to the formation of thin films with distinct, randomized side-by-side domains. Alternatively, processing at slower velocities in the evaporative regime results in the global alignment of PS-AuNRs. Processing speed and substrate surface energy afford tuning of the film's optical extinction of a given PS-AuNR via fine control of inter-rod distance and subsequent plasmonic coupling between neighboring nanorods. Because the concept of the polymer-grafted nanorod can be expanded to a variety of different polymer canopies, shapes, and core materials, the processing-structure relationships established in this work will have important implications on the future development of anisotropic nanostructure-based applications.

Projectile Impact Shock-Induced Deformation of One-Component Polymer Nanocomposite Thin Films.

Matrix-free assemblies of polymer-grafted nanoparticles (PGNs) enable mechanically robust materials for a variety of structural, electronic, and optical applications. Recent quasi-static mechanical studies have identified the key parameters that enhance canopy entanglement and promote plasticity of the PGNs below Tg. Here we experimentally explore the high-strain-rate shock impact behavior of polystyrene grafted NPs and compare their energy absorption capabilities to that of homopolystyrene for film thicknesses ranging from 75 to 550 nm and for impact velocities from 350 to 800 m/s. Modeling reveals that the initial shock compression results in a rapid temperature increase at the impact site. The uniformity of this heating is consistent with observations of greater kinetic energy absorption per mass (Ep*) of thinner films due to extensive visco-plastic deformation of molten film around the penetration site. Adiabatic heating is insufficient to raise the temperature at the exit surface of the thickest films resulting in increased strain localization at the impact periphery with less melt elongation. The extent and distribution of entanglements also influence Ep*. Structurally, each NP acts as a giant cross-link node, coupling surrounding nodes via the number of canopy chains per NP and the nature and number of entanglements between canopies anchored to different NPs. Load sharing via this dual network, along with geometrical factors such as film thickness, lead to extreme Ep* arising from the sequence of instantaneous adiabatic shock heating followed by visco-plastic drawing of the film by the projectile. These observations elucidate the critical factors necessary to create robust polymer-nanocomposite multifunctional films.

Autonomous materials discovery driven by Gaussian process regression with inhomogeneous measurement noise and anisotropic kernels.

A majority of experimental disciplines face the challenge of exploring large and high-dimensional parameter spaces in search of new scientific discoveries. Materials science is no exception; the wide variety of synthesis, processing, and environmental conditions that influence material properties gives rise to particularly vast parameter spaces. Recent advances have led to an increase in the efficiency of materials discovery by increasingly automating the exploration processes. Methods for autonomous experimentation have become more sophisticated recently, allowing for multi-dimensional parameter spaces to be explored efficiently and with minimal human intervention, thereby liberating the scientists to focus on interpretations and big-picture decisions. Gaussian process regression (GPR) techniques have emerged as the method of choice for steering many classes of experiments. We have recently demonstrated the positive impact of GPR-driven decision-making algorithms on autonomously-steered experiments at a synchrotron beamline. However, due to the complexity of the experiments, GPR often cannot be used in its most basic form, but rather has to be tuned to account for the special requirements of the experiments. Two requirements seem to be of particular importance, namely inhomogeneous measurement noise (input-dependent or non-i.i.d.) and anisotropic kernel functions, which are the two concepts that we tackle in this paper. Our synthetic and experimental tests demonstrate the importance of both concepts for experiments in materials science and the benefits that result from including them in the autonomous decision-making process.

Precise pitch-scaling of carbon nanotube arrays within three-dimensional DNA nanotrenches.

Precise fabrication of semiconducting carbon nanotubes (CNTs) into densely aligned evenly spaced arrays is required for ultrascaled technology nodes. We report the precise scaling of inter-CNT pitch using a supramolecular assembly method called spatially hindered integration of nanotube electronics. Specifically, by using DNA brick crystal-based nanotrenches to align DNA-wrapped CNTs through DNA hybridization, we constructed parallel CNT arrays with a uniform pitch as small as 10.4 nanometers, at an angular deviation <2° and an assembly yield >95%.

DNA-directed nanofabrication of high-performance carbon nanotube field-effect transistors.

Biofabricated semiconductor arrays exhibit smaller channel pitches than those created using existing lithographic methods. However, the metal ions within biolattices and the submicrometer dimensions of typical biotemplates result in both poor transport performance and a lack of large-area array uniformity. Using DNA-templated parallel carbon nanotube (CNT) arrays as model systems, we developed a rinsing-after-fixing approach to improve the key transport performance metrics by more than a factor of 10 compared with those of previous biotemplated field-effect transistors. We also used spatially confined placement of assembled CNT arrays within polymethyl methacrylate cavities to demonstrate centimeter-scale alignment. At the interface of high-performance electronics and biomolecular self-assembly, such approaches may enable the production of scalable biotemplated electronics that are sensitive to local biological environments.

A Low Energy Route to DNA-Wrapped Carbon Nanotubes via Replacement of Bile Salt Surfactants.

DNA-wrapped carbon nanotubes are a class of bionano hybrid molecules that have enabled carbon nanotube sorting, controlled assembly, and biosensing and bioimaging applications. The current method of synthesizing these hybrids via direct sonication of DNA/nanotube mixtures is time-consuming and not suitable for high-throughput synthesis and combinatorial sequence screening. Additionally, the direct sonication method does not make use of nanotubes presorted by extensively developed surfactant-based methods, is not effective for large diameter (>1 nm) tubes, and cannot maintain secondary and tertiary structural and functional domains present in certain DNA sequences. Here, we report a simple, quick, and robust process to produce DNA-wrapped carbon nanotube hybrids with nanotubes of broad diameter range and DNA of arbitrary sequence. This is accomplished by exchanging strong binding bile salt surfactant coating with DNA in methanol/water mixed solvent and subsequent precipitation with isopropyl alcohol. The exchange process can be completed within 10 min and converts over 90% nanotubes into the DNA wrapped form. Applying the exchange process to nanotubes presorted by surfactant-based methods, we show that the resulting DNA-wrapped carbon nanotubes can be further sorted to produce nanotubes with defined handedness, helicity, and endohedral filling. The exchange method greatly expands the structural and functional variety of DNA-wrapped carbon nanotubes and opens possibilities for DNA-directed assembly of structurally sorted nanotubes and high-throughput screening of properties that are controlled by the wrapping DNA sequences.

Differentiating Left- and Right-Handed Carbon Nanotubes by DNA.

New structural characteristics emerge when solid-state crystals are constructed in lower dimensions. This is exemplified by single-wall carbon nanotubes, which exhibit a degree of freedom in handedness and a multitude of helicities that give rise to three distinct types of electronic structures: metals, quasi-metals, and semiconductors. Here we report the use of intrinsically chiral single-stranded DNA to achieve simultaneous handedness and helicity control for all three types of nanotubes. We apply polymer aqueous two-phase systems to select special DNA-wrapped carbon nanotubes, each of which we argue must have an ordered DNA structure that binds to a nanotube of defined handedness and helicity and resembles a well-folded biomacromolecule with innate stereoselectivity. We have screened over 300 short single-stranded DNA sequences with palindrome symmetry, leading to the selection of more than 20 distinct carbon nanotube structures that have defined helicity and handedness and cover the entire chiral angle range and all three electronic types. The mechanism of handedness selection is illustrated by a DNA sequence that adopts two distinct folds on a pair of (6,5) nanotube enantiomers, rendering them large differences in fluorescence intensity and chemical reactivity. This result establishes a first example of functionally distinguishable left- and right-handed carbon nanotubes. Taken together, our work demonstrates highly efficient enantiomer differentiation by DNA and offers a first comprehensive solution to achieve simultaneous handedness and helicity control for all three electronic types of carbon nanotubes.

Intensity Ratio of Resonant Raman Modes for (n,m) Enriched Semiconducting Carbon Nanotubes.

Relative intensities of resonant Raman spectral features, specifically the radial breathing mode (RBM) and G modes, of 11, chirality-enriched, single-wall carbon nanotube (SWCNT) species were established under second-order optical transition excitation. The results demonstrate an under-recognized complexity in the evaluation of Raman spectra for the assignment of (n,m) population distributions. Strong chiral angle and mod dependencies affect the intensity ratio of the RBM to G modes and can result in misleading interpretations. Furthermore, we report five additional (n,m) values for the chirality-dependent G(+) and G(-) Raman peak positions and intensity ratios; thereby extending the available data to cover more of the smaller diameter regime by including the (5,4) second-order, resonance Raman spectra. Together, the Raman spectral library is demonstrated to be sufficient for decoupling G peaks from multiple species via a spectral fitting process, and enables fundamental characterization even in mixed chiral population samples.

Redox sorting of carbon nanotubes.

This work expands the redox chemistry of single-wall carbon nanotubes (SWCNTs) by investigating its role in a number of SWCNT sorting processes. Using a polyethylene glycol (PEG)/dextran (DX) aqueous two-phase system, we show that electron-transfer between redox molecules and SWCNTs triggers reorganization of the surfactant coating layer, leading to strong modulation of nanotube partition in the two phases. While the DX phase is thermodynamically more favored by an oxidized SWCNT mixture, the mildly reducing PEG phase is able to recover SWCNTs from oxidation and extract them successively from the DX phase. Remarkably, the extraction order follows SWCNT bandgap: semiconducting nanotubes of larger bandgap first, followed by semiconducting nanotubes of smaller bandgap, then nonarmchair metallic tubes of small but nonvanishing bandgap, and finally armchair metallic nanotubes of zero bandgap. Furthermore, we show that redox-induced surfactant reorganization is a common phenomenon, affecting nanotube buoyancy in a density gradient field, affinity to polymer matrices, and solubility in organic solvents. These findings establish redox modulation of surfactant coating structures as a general mechanism for tuning a diverse range of SWCNT sorting processes and demonstrate for the first time that armchair and nonarmchair metallic SWCNTs can be separated by their differential response to redox.

Variance Spectroscopy.

Spectroscopic analysis and study of nanoparticle samples is often hampered by structural diversity that presents a complex superposition of spectral signatures. By probing the spectra of small volumes within dilute samples, we can expose statistical variations in composition to obtain information unavailable from bulk spectroscopy. This new approach is demonstrated using fluorescence spectra of unsorted single-walled carbon nanotube samples to deduce structure-specific abundances and emissive efficiencies. Furthermore, correlations between intensity variations at different wavelengths provide two-dimensional covariance maps that isolate the spectra of homogeneous subpopulations. Covariance analysis is also a sensitive probe of particle aggregation. It shows that well-dispersed nanotube samples can spontaneously form loose aggregates of a type not previously recognized. Variance spectroscopy is a simple and practical technique that should find application in many nanoparticle studies.

Directly measured optical absorption cross sections for structure-selected single-walled carbon nanotubes.

We have measured peak and spectrally integrated absolute absorption cross sections for the first (E11) and second (E22) optical transitions of seven semiconducting single-walled carbon nanotube (SWCNT) species in bulk suspensions. Species-specific concentrations were determined using short-wave IR fluorescence microscopy to directly count SWCNTs in a known sample volume. Measured cross sections per atom are inversely related to nanotube diameter. E11 cross sections are larger for mod 1 species than for mod 2; the opposite is found for E22.

Chromatic aberration short-wave infrared spectroscopy: nanoparticle spectra without a spectrometer.

A new method is described for measuring the short-wave infrared (SWIR) emission wavelengths of numerous individual nanoparticles without using a dedicated spectrometer. Microscope objectives designed for use at visible wavelengths often show severe axial chromatic aberration in the SWIR. This makes coplanar objects emitting at different SWIR wavelengths appear to focus at different depths. After this aberration has been calibrated for a particular objective lens, the depth at which an emissive nanoparticle appears brightest and best focused can be used to deduce its peak emission wavelength. The method is demonstrated using a dilute, structurally polydisperse sample of single-walled carbon nanotubes deposited onto a microscope slide. Discrete emission centers in this sample have different peak wavelengths corresponding to specific nanotube structural species. A set of images was recorded at stepped focus settings and analyzed to find the sharpest focus depth of each nanotube. The chromatic aberration calibration curve converted these depths into peak emission wavelengths with a spectral resolution better than 3 nm, allowing identification of each nanotube's structure. Chromatic aberration spectroscopy is a practical tool for using existing microscopic equipment to extract significant spectral information on coplanar nanoparticle samples that emit or scatter light.

Measuring single-walled carbon nanotube length distributions from diffusional trajectories.

A new method is demonstrated for measuring the length distributions of dispersed single-walled carbon nanotube (SWCNT) samples by analyzing diffusional motions of many individual nanotubes in parallel. In this method, termed "length analysis by nanotube diffusion" (LAND), video sequences of near-IR fluorescence microscope images showing many semiconducting SWCNTs are recorded and processed by custom image analysis software. This processing locates the individual nanotubes, tracks their translational trajectories, computes the corresponding diffusion coefficients, and converts those values to nanotube lengths. The deduced length values are then compiled into a histogram of lengths present in the sample. By using specific excitation wavelengths and emission filters, this analysis is performed on selected (n,m) structural species. The new LAND method has been found to give distributions in very good agreement with those obtained by conventional AFM analysis of the same samples. Because it is fluorescence-based, LAND monitors only semiconducting, relatively pristine SWCNTs. However, it is less sensitive to artifacts from impurities and bundled nanotubes than AFM or light scattering methods. In addition, samples can be analyzed with less time and operator attention than by AFM. LAND is a promising alternative method for characterizing length distributions of SWCNTs in liquid suspension.