Length Fractionation Research Articles

Universalized and robust length separation of carbon and boron nitride nanotubes with improved polymer depletion-based fractionation.

Partitioning nanoparticles by shape and dimension is paramount for advancing nanomaterial standardization, fundamental colloidal investigations, and technologies such as biosensing and digital electronics. Length-separation methods for single-walled carbon nanotubes (SWCNTs) have historically incurred trade-offs in precision and mass throughput, and boron nitride nanotubes (BNNTs) are a rapidly emerging material analogue. We extend and detail a polymer precipitation-based method to fractionate populations of either nanotube type at significant mass scale for four distinct nanotube sources of increasing average diameter (0.7 nm to >2 nm). Such separations result in a supernant phase containing shorter nanotubes and a pellet phase containing the longer nanotubes, with the threshold length for depletion decreasing with increasing polymer concentration. Cross-comparison through analytical ultracentrifugation, spectroscopy, and microscopy versus applied polymer concentration show tailorable and precise length fractionation for 100 nm through >1 μm rod lengths, with fractionation also designable to remove non-nanotube impurities. The threshold length of depletion is further found to increase for decreasing nanotube diameter at fixed polymer concentration, a finding consistent with scaling attributable to nanotube radial excluded volume. The capabilities demonstrated herein promise to significantly advance nanotube implementation within the scientific community.

Length-Dependent Enantioselectivity of Carbon Nanotubes by Gel Chromatography

High-purity enantiomer separation of chiral single-wall carbon nanotubes (SWCNTs) remains a challenge compared with electrical type and chirality separations due to the limited selectivities for both chirality and handedness, which is important for an exploration of their properties and practical applications. Here, we performed length fractionation for enantiomer-purified SWCNTs and found a phenomenon in which the enantioselectivities were higher for longer nanotubes than for shorter nanotubes due to length-dependent interactions with the gel medium, which provided an effective strategy of controlling nanotube length for high-purity enantiomer separation. Furthermore, we employed a gentler pulsed ultrasonication instead of traditional vigorous ultrasonication for preparation of a low-defect long SWCNT dispersion and achieved the enantiomer separation of single-chirality (6,5) SWCNTs with an ultrahigh enantiomeric purity of up to 98%, which was determined by using the linear relationship between the normalized circular dichroism intensity and the enantiomeric purity. Compared with all results reported previously, the present enantiomeric purity was significantly higher and reached the highest level reported to date. Due to the ultrahigh selectivity in both chirality and handedness, the two obtained enantiomers exhibited perfect symmetry in their circular dichroism spectra, which offers standardization for characterizations and evaluations of SWCNT enantiomers.

Improved volume variable cluster model method for crystal-lattice optimization: effect on isotope fractionation factor

The isotopic fractionation factor and element partition coefficient can be calculated only after the geometric optimization of the molecular clusters is completed. Optimization directly affects the accuracy of some parameters, such as the average bond length, molecular volume, harmonic vibrational frequency, and other thermodynamic parameters. Here, we used the improved volume variable cluster model (VVCM) method to optimize the molecular clusters of a typical oxide, quartz. We documented the average bond length and relative volume change. Finally, we extracted the harmonic vibrational frequencies and calculated the equilibrium fractionation factor of the silicon and oxygen isotopes. Given its performance in geometrical optimization and isotope fractionation factor calculation, we further applied the improved VVCM method to calculate isotope equilibrium fractionation factors of Cd and Zn between the hydroxide (Zn–Al layered double hydroxide), carbonate (cadmium-containing calcite) and their aqueous solutions under superficial conditions. We summarized a detailed procedure and used it to re-evaluate published theoretical results for cadmium-containing hydroxyapatite, emphasizing the relative volume change for all clusters and confirming the optimal point charge arrangement (PCA). The results showed that the average bond length and isotope fractionation factor are consistent with those published in previous studies, and the relative volume changes are considerably lower than the results calculated using the periodic boundary method. Specifically, the average Si–O bond length of quartz was 1.63 Å, and the relative volume change of quartz centered on silicon atoms was − 0.39%. The average Zn–O bond length in the Zn–Al-layered double hydroxide was 2.10 Å, with a relative volume change of 1.96%. Cadmium-containing calcite had an average Cd–O bond length of 2.28 Å, with a relative volume change of 0.45%. At 298 K, the equilibrium fractionation factors between quartz, Zn–Al-layered double hydroxide, cadmium-containing calcite, and their corresponding aqueous solutions were Delta ^{30/28} {text{Si}}_{{{text{Qtz-H}}_{4} {text{SiO}}_{4} }} = 2.20{permil} , Delta^{18/16} {text{O}}_{ {text{Qtz}}{-} ( {text{H}}_{2} {text{O}} )_{text{n}}} = 36.05{permil}, Delta^{66/64} {text{Zn}}_{ {text{Zn}} {-} {text{Al LDH-Zn}} ( {text{H}}_{2} {text{O}} )_{text{n}}^{2+}} = 1.12{permil} and Delta^{114/110} {text{Cd}}_{ {text{(Cd--Cal)-Cd}} ( {text{H}}_{2} {text{O}} )_ {text{n}}^{2 +} } = - 0.26{permil} respectively. These results strongly support the reliability of the improved VVCM method for geometric optimization of molecular clusters.

Angular segregation of fibres in pipe flow: floc formation and utilization for length-based fibre separation

Cellulose fibres are prone to flocculate and form aggregates that are deformable by the hydrodynamic stress. In this work I document for coiled pipe flow, known to have secondary motion in the pipe cross-sectional plane, an accumulation of fibre flocs and fibre aggregates at the outer bend. That is the segregation into a section in the pipe cross-section and hence presents a case of angular segregation. The segregation was studied for non-coherent crowded fibre flocs. For that, segregation benefited from fibre concentration and suffered from increased hydrodynamic stress expressed by increasing Reynolds number. Based on the observed segregation of fibres a flow splitter was designed that separated the flow at 1/3 of the tube diameter measured from the inner bend. The outer bend suspension length-weighted fibre length was found to increase. For the best case in this work, the difference between outer and inner bend relative to the feed fibre length was 22%. As for radial and axial segregation, which are known, also angular segregation is fibre-length sensitive. As such it can be exploited for length fractionation of networking and aggregating elongated particles, for example fibres.

A facile and low-cost length sorting of single-wall carbon nanotubes by precipitation and applications for thin-film transistors.

Semiconducting single-wall carbon nanotubes (SWCNTs) with long lengths are highly desirable for many applications such as thin-film transistors and circuits. Previously reported length sorting techniques usually require sophisticated instrumentation and are hard to scale up. In this paper, we report for the first time a general phenomenon of a length-dependent precipitation of surfactant-dispersed carbon nanotubes by polymers, salts, and their combinations. Polyelectrolytes such as polymethacrylate (PMAA) and polystyrene sulfonate (PSS) are found to be especially effective on cholate and deoxycholate dispersed SWCNTs. By adding PMAA to these nanotube dispersions in a stepwise fashion, we have achieved nanotube precipitation in a length-dependent order: first nanotubes with an average length of 650 nm, and then successively of 450 nm, 350 nm, and 250 nm. A similar effect of nanotube length sorting has also been observed for PSS. To demonstrate the utility of the length fractionation, the 650 nm-long nanotube fraction was subjected to an aqueous two-phase separation to obtain semiconducting enriched nanotubes. Thin-film transistors fabricated with the resulting semiconducting SWCNTs showed a carrier mobility up to 18 cm(2) (V s)(-1) and an on/off ratio up to 10(7). Our result sheds new light on the phase behavior of aqueous nanotube dispersions under high concentrations of polymers and salts, and offers a facile, low-cost, and scalable method to produce length sorted semiconducting nanotubes for macroelectronics applications.

Magnesium isotope fractionation between brucite [Mg(OH)2] and Mg aqueous species: Implications for silicate weathering and biogeochemical processes

Brucite, with its octahedral structure, has a lattice configuration that is similar to the Mg-bearing octahedral layers in phyllosilicates. Understanding stable Mg isotope fractionation between brucite and aqueous solution therefore bears on interpretation of Mg isotope data in natural weathering systems. In this study, we experimentally determined Mg isotope fractionation between brucite and two Mg aqueous species, the free Mg aquo ion ([Mg(OH2)6]2+) and EDTA-bonded Mg (Mg-EDTA2−). Results from recrystallization and brucite synthesis experiments suggest mild preferential partitioning of light Mg isotopes into brucite compared to Mg aquo ions at low temperatures, where measured ΔMgbrucite-Mg2+26 fractionation increased from ca. −0.3‰ at 7 °C, to ca. −0.2‰ at 22 °C, to ca. 0‰ at 40 °C. MgO hydrolysis experiments in EDTA-bearing solutions suggest that the ΔMgbrucite-Mg-EDTA26 fractionation is ⩾+2.0‰ at 22 °C, indicating that light Mg isotopes strongly partition into Mg-EDTA complex relative to brucite, as well as relative to Mg aquo ions. Magnesium atoms in brucite, Mg aquo ions, and Mg-EDTA complexes are all octahedrally coordinated, and the measured Mg isotope fractionations correlate with average bond lengths for Mg. Aqueous Mg ions have the shortest bond length among the three phases, and enrich heavy Mg isotopes relative to brucite and Mg-EDTA. In contrast, Mg-EDTA has the longest average bond length for Mg, and enriches light Mg isotopes relative to Mg aquo ions and brucite; the relatively long Mg-EDTA bond suggests that organically bound Mg may commonly have low 26Mg/24Mg ratios, which may explain proposed “vital” effects for stable Mg isotopes. Such relations between bond length and Mg isotope fractionation could be extended to other phyllosilicates such as serpentine- and clay-group minerals where Mg is also octahedrally coordinated.

Length Fractionation of Boron Nitride Nanotubes Using Creamed Oil-in-Water Emulsions

The fractionation by length of multiwalled boron nitride nanotubes (BNNTs) was achieved by emulsification and creaming of an oil/water/surfactant mixture. The length separation is based on the fact that nanoparticle-coated oil droplets polydisperse in size move toward the upper surface or the bottom of an emulsified mixture depending on the density of the droplets, such that droplets of different sizes are located at different heights. By sampling heightwise an unstable hexane/water/Tween 20/BNNT (1-20 μm long) emulsion, we observed that the lengths of the BNNTs adsorbed on the droplets display a strong correlation with the droplets sizes, thus leading to selective separation of the BNNT lengths, as confirmed by dark-field optical imaging and dynamic light scattering. This method may potentially be extended to other high aspect ratio nanomaterials exhibiting emulsification properties similar to those of BNNTs.

High-Resolution Length Fractionation of Surfactant-Dispersed Carbon Nanotubes

Length fractionation of colloidal single-wall carbon nanotube (SWCNT) dispersions is required for many studies. Size-exclusion chromatography (SEC) has been developed as a reliable method for high-resolution length fractionation of DNA-dispersed SWCNTs but has not been applied to surfactant-dispersed SWCNTs due to their lower dispersion stability and tendency to adsorb onto SEC stationary phases. Here, we report that SEC length fractionation can be achieved for bile salt dispersed SWCNTs by using porous silica-based beads as the stationary phase and bile salt solution as the mobile phase. We demonstrate that the SEC length sorting method can be combined with existing ultracentrifugation SWCNT sorting methods to produce "orthogonally sorted" samples, including length sorted semiconducting SWCNTs, which are important for electronics applications as well as length sorted empty-core SWCNTs. Importantly, we show that unlike simple length fractionation by SEC or any other method, orthogonal sorting produces samples of consistent quality for different length fractions, with similar UV-vis-nearIR absorption and Raman spectral features.

Length-dependent optical properties of single-walled carbon nanotube samples

Contradictory findings have been reported on the length dependence of optical absorption cross sections and fluorescence quantum yields in single-walled carbon nanotubes (SWCNTs). To clarify these points, studies have been made on bulk SWCNT dispersions subjected to length fractionation by electrophoretic separation or by ultrasonication-induced scission. Fractions ranged from ca. 120 to 760nm in mean length. Samples prepared by shear-assisted dispersion were subsequently shortened by ultrasonic processing. After accounting for processing-induced changes in the surfactant absorption background, SWCNT absorption was found constant within ±11% as average nanotube length changed by a factor of 3.8. This indicates that the absorption cross-section per carbon atom is not length dependent. By contrast, in length fractions prepared by both methods, the bulk fluorescence efficiency or average quantum yield increased with SWCNT average length and approached an apparent asymptotic limit near 1μm. This result is interpreted as reflecting the combined contributions of exciton quenching by sidewall defects and by the ends of shorter nanotubes.

Isotropic–nematic phase separation and demixing in mixtures of spherical nanoparticles with length‐polydisperse nanorods

AbstractAn extension of Onsager theory is developed to simulate isotropic–nematic phase separation in a mixture of spheres with length‐polydisperse system of rods. This work is motivated by recent experimental data on nanorod liquid crystals. Prior theoretical investigations indicate that both polydispersity and the presence of spheres should increase the biphasic–nematic phase transition, that is, the nematic cloud point. Results indicate that the phase diagrams undergo drastic changes depending upon both particle geometry and rod length polydispersity. The key geometric factor is the ratio between the sphere diameter and the rod diameter. In general, length fractionation is enhanced by the addition of spheres, which may be experimentally advantageous for separating short nanorods from a polydisperse population. Simulation results also indicate that the nematic cloud and shadow curves may cross one another because of the scarcity of spheres in the shadow phase. In general, these results do indicate that the nematic cloud point increases as a function of sphere loading; however, in certain areas of phase space, this relationship is nonmonotonic such that the nematic cloud point may actually decrease with the addition of spheres. This work has application to a wide range of nanoparticle systems, including mixtures of spherical nanoparticles with nanorods or nanotubes. Additionally, a number of nonspherical particles and structures may behave as spheres, including crumpled graphene and tightly coiled polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

Molecular-Crowding-Induced Clustering of DNA-Wrapped Carbon Nanotubes for Facile Length Fractionation

Emerging applications require single-wall carbon nanotubes (SWCNTs) of well-defined length. Yet the use of length-defined SWCNTs is limited, in part due to the lack of an easily accessible materials preparation method. Here, we present a new strategy for SWCNT length fractionation based on molecular crowding induced cluster formation. We show that the addition of polyethylene glycol (PEG) as a crowding agent into DNA-wrapped SWCNT dispersion leads to the formation of reversible, nematic, and rodlike microclusters, which can be collected by gentle centrifugation. Since shorter SWCNTs form clusters at higher polyethylene glycol concentration, gradual increase in PEG concentration results in length fractionated SWCNTs. Using atomic force microscopy (AFM) we show that fractions with average lengths of 60-500 nm and standard deviations of 30-40% can be obtained. The concept of molecular-crowding-based fractionation should be applicable to other nanoparticle dispersions.

Modeling the phase behavior of polydisperse rigid rods with attractive interactions with applications to single-walled carbon nanotubes in superacids

The phase behavior of rodlike molecules with polydisperse length and solvent-mediated attraction and repulsion is described by an extension of the Onsager theory for rigid rods. A phenomenological square-well potential is used to model these long-range interactions, and the model is used to compute phase separation and length fractionation as a function of well depth and rod concentration. The model closely captures experimental data points for isotropic/liquid crystalline phase coexistence of single-walled carbon nanotubes (SWCNTs) in superacids. The model also predicts that the isotropic-biphasic boundary approaches zero as the acid strength diminishes, with the possibility of coexistence of isotropic and liquid crystalline phases at very low concentrations; this counterintuitive prediction is confirmed experimentally. Experimental deviations from classical theories for rodlike liquid crystals are explained in terms of polydispersity and the balance between short-range repulsion and long-range attractions. The predictions of the model also hold practical importance for applications of SWCNT/superacid solutions, particularly in the processing of fibers and films from liquid crystalline SWCNT/superacid mixtures.

Concomitant Length and Diameter Separation of Single-Walled Carbon Nanotubes

Gel electrophoresis and column chromatography conducted on individually dispersed, ultrasonicated single-walled carbon nanotubes yield simultaneous separation by tube length and diameter. Electroelution after electrophoresis is shown to produce highly resolved fractions of nanotubes with average lengths between 92 and 435 nm. Separation by diameter is concomitant with length fractionation, and nanotubes that have been cut shortest also possess the greatest relative enrichments of large-diameter species. Longer sonication time causes increased electrophoretic mobility in the gels; thus, ultrasonic processing determines the degree of both length and diameter separation of the nanotubes. The relative quantum yield decreases nonlinearly as the nanotube length becomes shorter. These techniques constitute a preparative, scalable method for separating nanotubes by two important attributes required for electronic and sensor applications.

Long-range electrical contacting of redox enzymes by SWCNT connectors.

Long-range electrical contacting of redox enzymes by SWCNT connectors.

Genomics: the science and technology behind the human genome project

DNA Chemistry and Biology. A Genome Overview at the Level of Chromosomes. Analysis of DNA Sequences by Hybridization. Polymerase Chain Reaction and Other Methods for In Vitro DNA Amplification. Principles of DNA Electrophoresis. Genetic Analysis. Cytogenetics and Pseudogenetics. Physical Mapping. Enhanced Methods for Physical Mapping. DNA Sequencing: Current Tactics. Strategies for Large--Scale DNA Sequencing. Future DNA Sequencing Without Length Fractionation. Finding Genes and Mutations. Sequence--Specific Manipulation of DNA. Results and Implications of Large--Scale DNA Sequencing. Appendix. Index.