Free energetics of carbon nanotube association in pure and aqueous ionic solutions.
ABSTRACT: Carbon nanotubes are a promising platform across a broad spectrum of applications ranging from separations technology, drug delivery, to bio(electronic) sensors. Proper dispersion of carbon nanotube materials is important to retaining the electronic properties of nanotubes. Experimentally it has been shown that salts can regulate the dispersing properties of CNTs in aqueous system with surfactants (Niyogi, S.; Densmore, C. G.; Doorn, S. K. J. Am. Chem. Soc.2009, 131, 1144-1153); details of the physicochemical mechanisms underlying such effects continue to be explored. We address the effects of inorganic monovalent salts (NaCl and NaI) on dispersion stability of carbon nanotubes.We perform all-atom molecular dynamics simulations using nonpolarizable interaction models to compute the potential of mean force between two (10,10) single-walled carbon nanotubes (SWNTs) in the presence of NaCl/NaI and compare to the potential of mean force between SWNTs in pure water. Addition of salts enhances stability of the contact state between two SWNT's on the order of 4 kcal/mol. The ion-specific spatial distribution of different halide anions gives rise to starkly different contributions to the free energy stability of nanotubes in the contact state. Iodide anion directly stabilizes the contact state to a much greater extent than chloride anion. The enhanced stability arises from the locally repulsive forces imposed on nanotubes by the surface-segregated iodide anion. Within the time scale of our simulations, both NaI and NaCl solutions stabilize the contact state by equivalent amounts. The marginally higher stability for contact state in salt solutions recapitulates results for small hydrophobic solutes in NaCl solutions (Athawale, M. V.; Sarupria, S.; Garde, S. J. Phys. Chem. B2008, 112, 5661-5670) as well as single-walled carbon nanotubes in NaCl and CaCl2 aqueous solutions.
Project description:Aggregation kinetics of chiral-specific semiconducting single-walled carbon nanotubes (SWNTs) was systematically studied through time-resolved dynamic light scattering. Varied monovalent (NaCl) and divalent (CaCl(2)) electrolyte composition was used as background solution chemistry. Suwannee River humic acid (SRHA) was used to study the effects of natural organic matter on chirally separated SWNT aggregation. Increasing salt concentration and introduction of divalent cations caused aggregation of SWNT clusters by suppressing the electrostatic repulsive interaction from the oxidized surfaces. The (6,5) SWNTs, i.e., SG65, with relatively lower diameter tubes compared to (7,6), i.e., SG76, showed substantially higher stability (7- and 5-fold for NaCl and CaCl(2), respectively). The critical coagulation concentration (CCC) values were 96 and 13 mM NaCl in the case of NaCl and 2.8 and 0.6 mM CaCl(2) for SG65 and SG76, respectively. The increased tube diameter for (7,6) armchair SWNTs likely presented with higher van der Waals interaction and thus increased the aggregation propensity substantially. The presence of SRHA enhanced SWNT stability in divalent CaCl(2) environment through steric interaction from adsorbed humic molecules; however showed little or no effects for monovalent NaCl. The mechanism of aggregation-describing favorable interaction tendencies for (7,6) SWNTs-is probed through ab initio molecular modeling. The results suggest that SWNT stability can be chirality dependent in typical aquatic environment.
Project description:Utilization of single-walled carbon nanotubes (SWNTs) in high-end applications hinges on separating metallic (met-) from semiconducting (sem-) SWNTs. Surfactant amines, like octadecylamine (ODA) have proven instrumental for the selective extraction of sem-SWNTs from tetrahydrofuran (THF) nanotube suspensions. The chemical shift differences along the tail of an asymmetric, diacetylenic surfactant amine were used to probe the molecular dynamics in the presence and absence of nanotubes via NMR. The results suggest that the surfactant amine head is firmly immobilized onto the nanotube surface together with acidic water, while the aliphatic tail progressively gains larger mobility as it gets farther from the SWNT. X-ray and high-resolution TEM studies indicate that the sem-enriched sample is populated mainly by small nanotube bundles containing ca. three SWNTs. Molecular simulations in conjunction with previously determined HNO(3)/H(2)SO(4) oxidation depths for met- and sem-SWNTs indicate that the strong pinning of the amine surfactants on the sem-enriched SWNTs bundles is a result of a well-ordered arrangement of nitrate/amine salts separated with a monomolecular layer of H(2)O. Such continuous 2D arrangement of nitrate/amine salts shields the local environment adjacent to sem-enriched SWNTs bundles and maintains an acidic pH that preserves nanotube oxidation (i.e., SWNT(n+)). This, in turn, results in strong interactions with charge-balancing NO(3)(-) counterions that through their association with neutralized surfactant amines provide effective THF dispersion and consequent sem enrichment.
Project description:Aiming to improve understanding of the mechanisms behind specific anion effects in biological systems we have studied the effects of sodium salts of simple monovalent anions belonging to the Hofmeister series on the bilayers of the zwitterionic lipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine using small-angle x-ray scattering and the osmotic stress technique. NaCl, NaBr, NaNO(3), NaI, and NaSCN were used in this investigation. The electrolytes were found to swell the bilayers and to increase the area per lipid headgroup at each value of the osmotic pressure, suggesting the association of anions with the bilayer-lipid interfaces. The effects follow the Hofmeister series with SCN(-) inducing the most pronounced changes. "Ion competition" experiments with mixed NaI/NaCl solutions at total salinity 0.1 and 0.5 M revealed that the effect of ions on the lipid equation-of-state is roughly linear at low concentrations, but strongly nonlinear at high concentrations. The experimental results are fitted in a companion article to provide "binding" or "partitioning" constants of anions in the lipid bilayers.
Project description:Single-walled carbon nanotubes' (SWNT) effectiveness in applications is enhanced by debundling or stabilization. Anionic surfactants are known to effectively stabilize SWNTs. However, the role of specific chirality on surfactant-stabilized SWNT aggregation has not been studied to date. The aggregation behavior of chirally enriched (6,5) and (7,6) semiconducting SWNTs, functionalized with three anionic surfactants-sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), and sodium deoxycholate (SDOCO)-was evaluated with time-resolved dynamic light scattering. A wide range of mono- (NaCl) and di-valent (CaCl2) electrolytes as well as a 2.5 mg TOC/L Suwannee River humic acid (SRHA) were used as background chemistry. Overall, SDBS showed the most effectiveness in SWNT stability, followed by SDOCO and SDS. However, the relatively larger diameter (7,6) chiral tubes compromised the surfactant stability, compared to (6,5) chiral enrichment, due to enhanced van der Waals interaction. The presence of di-valent electrolytes overshadowed the chirality effects and resulted in similar aggregation behavior for both the SWNT samples. Molecular modeling results enumerated key differences in surfactant conformation on SWNT surfaces and identified interaction energy changes between the two chiralities to delineate aggregation mechanisms. The stability of SWNTs increased in the presence of SRHA under 10 mM monovalent and mixed electrolyte conditions. The results suggest that change in chirality can overcome surfactant stabilization of semiconducting SWNTs. SWNT stability can also be strongly influenced by the anionic surfactant structure.
Project description:The functionalization of semiconducting single-walled carbon nanotubes (SWNTs) with sp3 defects that act as luminescent exciton traps is a powerful means to enhance their photoluminescence quantum yield (PLQY) and to add optical properties. However, the synthetic methods employed to introduce these defects are currently limited to aqueous dispersions of surfactant-coated SWNTs, often with short tube lengths, residual metallic nanotubes, and poor film-formation properties. In contrast to that, dispersions of polymer-wrapped SWNTs in organic solvents feature unrivaled purity, higher PLQY, and are easily processed into thin films for device applications. Here, we introduce a simple and scalable phase-transfer method to solubilize diazonium salts in organic nonhalogenated solvents for the controlled reaction with polymer-wrapped SWNTs to create luminescent aryl defects. Absolute PLQY measurements are applied to reliably quantify the defect-induced brightening. The optimization of defect density and trap depth results in PLQYs of up to 4% with 90% of photons emitted through the defect channel. We further reveal the strong impact of initial SWNT quality and length on the relative brightening by sp3 defects. The efficient and simple production of large quantities of defect-tailored polymer-sorted SWNTs enables aerosol-jet printing and spin-coating of thin films with bright and nearly reabsorption-free defect emission, which are desired for carbon nanotube-based near-infrared light-emitting devices.
Project description:Isotopic, hydrogen-to-deuterium substitution has been an invaluable tool in the characterization of small molecules and biological nanostructures. The natural variability of most inorganic nanomaterials has hindered the use of isotopic substitution in gaining meaningful insights into their structure. The ideal helical wrapping of a flavin mononucleotide (FMN) around (8,6)-SWNTs (single-walled carbon nanotubes) is presently utilized to probe isotopically dependent intermolecular interactions. The facile proton-to-deuterium exchange of the imide group of FMN enabled us to alter the intermolecular stability of the helix depending on the surrounding solvent (i.e., H2O vs D2O). Our studies show that FMN-dispersed (8,6)-SWNTs exhibit greater stability in D2O than in H2O. The higher complex stability in D2O was verified on the basis of (i) FMN helix replacement with SDBS (sodium dodecylbenzenesulfate) and (ii) thermal- and (iii) pH-induced helix dissociation. This is in agreement with the previously observed stronger amide H-bonding of proteins in D2O, and to the best of our knowledge, it demonstrates the architectural fidelity of FMN-wrapped SWNTs, which is expected to enhance the assembly repertoire of carbon nanotubes further.
Project description:Carbon nanotubes are promising new materials for molecular delivery in biological systems. The long-term fate of nanotubes intravenously injected into animals in vivo is currently unknown, an issue critical to potential clinical applications of these materials. Here, using the intrinsic Raman spectroscopic signatures of single-walled carbon nanotubes (SWNTs), we measured the blood circulation of intravenously injected SWNTs and detect SWNTs in various organs and tissues of mice ex vivo over a period of three months. Functionalization of SWNTs by branched polyethylene-glycol (PEG) chains was developed, enabling thus far the longest SWNT blood circulation up to 1 day, relatively low uptake in the reticuloendothelial system (RES), and near-complete clearance from the main organs in approximately 2 months. Raman spectroscopy detected SWNT in the intestine, feces, kidney, and bladder of mice, suggesting excretion and clearance of SWNTs from mice via the biliary and renal pathways. No toxic side effect of SWNTs to mice was observed in necropsy, histology, and blood chemistry measurements. These findings pave the way to future biomedical applications of carbon nanotubes.
Project description:The influence of single-walled carbon nanotubes enriched in semiconductor (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of polyaniline (PANI), electrosynthesized in the presence of the H2SO4 and HCl solutions, is reported. The emission bands peaked at 407-418 and 440-520?nm indicate that the electropolymerization of aniline (ANI) leads to the formation of short and longer macromolecular chains (MCs), respectively. We demonstrate that the reaction product consists of ANI tetramers (TT) and trimers (TR) as well as PANI-salt. Using Raman scattering and IR absorption spectroscopy, a covalent functionalization of SWNTs with shorter and longer MCs of PANI-salt is demonstrated. The presence of S-SWNTs and M-SWNTs induces a decrease in ANI TT weight in the reaction product mass consisting in S-SWNTs and M-SWNTs covalently functionalized with PANI-emeraldine salt (ES) and PANI-leucoemeraldine salt (LS), respectively. A PANI PL quenching is reported to be induced of the S-SWNTs and M-SWNTs. A de-excitation mechanism is proposed to explain PANI PL quenching.
Project description:The unique properties of carbon nanotubes have made them the material of choice for many current and future industrial applications. As a consequence of the increasing development of nanotechnology, carbon nanotubes show potential threat to health and environment. Therefore, development of efficient method for detection of carbon nanotubes is required. In this work, we have studied the interaction of indopentamethinedioxaborine dye (DOB-719) and single-walled carbon nanotubes (SWNTs) using absorption and photoluminescence (PL) spectroscopy. In the mixture of the dye and the SWNTs we have revealed new optical features in the spectral range of the intrinsic excitation of the dye due to resonance energy transfer from DOB-719 to SWNTs. Specifically, we have observed an emergence of new PL peaks at the excitation wavelength of 735 nm and a redshift of the intrinsic PL peaks of SWNT emission (up to 40 nm) in the near-infrared range. The possible mechanism of the interaction between DOB-719 and SWNTs has been proposed. Thus, it can be concluded that DOB-719 dye has promising applications for designing efficient and tailorable optical probes for the detection of SWNTs.
Project description:Carbon nanotubes are capable of penetrating the cell membrane and are widely considered as potential carriers for gene or drug delivery. Because the C-C and C=C bonds in carbon nanotubes are nonpolar, functionalization is required for carbon nanotubes to interact with genes or drugs as well as to improve their biocompatibility. In this study, polyethylenimine (PEI)-functionalized single-wall (PEI-NH-SWNTs) and multiwall carbon nanotubes (PEI-NH-MWNTs) were produced by direct amination method. PEI functionalization increased the positive charge on the surface of SWNTs and MWNTs, allowing carbon nanotubes to interact electrostatically with the negatively charged small interfering RNAs (siRNAs) and to serve as nonviral gene delivery reagents. PEI-NH-MWNTs and PEI-NH-SWNTs had a better solubility in water than pristine carbon nanotubes, and further removal of large aggregates by centrifugation produced a stable suspension of reduced particle size and improved homogeneity and dispersity. The amount of grafted PEI estimated by thermogravimetric analysis was 5.08% (w/w) and 5.28% (w/w) for PEI-NH-SWNTs and PEI-NH-MWNTs, respectively. For the assessment of cytotoxicity, various concentrations of PEI-NH-SWNTs and PEI-NH-MWNTs were incubated with human cervical cancer cells, HeLa-S3, for 48 h. PEI-NH-SWNTs and PEI-NH-MWNTs induced cell deaths in a dose-dependent manner but were less cytotoxic compared to pure PEI. As determined by electrophoretic mobility shift assay, siRNAs directed against glyceraldehyde-3-phosphate dehydrogenase (siGAPDH) were completely associated with PEI-NH-SWNTs or PEI-NH-MWNTs at a PEI-NH-SWNT/siGAPDH or PEI-NH-MWNT/siGAPDH mass ratio of 80:1 or 160:1, respectively. Furthermore, PEI-NH-SWNTs and PEI-NH-MWNTs successfully delivered siGAPDH into HeLa-S3 cells at PEI-NH-SWNT/siGAPDH and PEI-NH-MWNT/siGAPDH mass ratios of 1:1 to 20:1, resulting in suppression of the mRNA level of GAPDH to an extent similar to that of DharmaFECT, a common transfection reagent for siRNAs. Our results indicate that the PEI-NH-SWNTs and PEI-NH-MWNTs produced in this study are capable of delivering siRNAs into HeLa-S3 cells to suppress gene expression and may therefore be considered as novel nonviral gene delivery reagents.