Carbon nanotubes: are they dispersed or dissolved in liquids?

Carbon nanotubes (CNTs) constitute a novel class of nanomaterials with remarkable applications in diverse domains. However, the main intrincsic problem of CNTs is their insolubility or very poor solubility in most of the common solvents. The basic key question here is: are carbon nanotubes dissolved or dispersed in liquids, specifically in water? When analyzing the scientific research articles published in various leading journals, we found that many researchers confused between "dispersion" and "solubilization" and use the terms interchangeably, particularly when stating the interaction of CNTs with liquids. In this article, we address this fundamental issue to give basic insight specifically to the researchers who are working with CNTs as well asgenerally to scientists who deal with nano-related research domains.Among the various nanomaterials, CNTs gained widespread attention owing to their exceptional properties, good chemical stability, and large surface area [1,2]. CNTs are extremely thin tubes and feature an extremely enviable combination of mechanical, thermal, electrical, and optical properties. Their size, shape, and properties construct them as prime contenders for exploiting the growth of a potentially revolutionary material for diverse applications.Nevertheless, the main intrinsic drawback of CNTs is their insolubility or extremely poor solubility in most of the common solvents due to their hydrophobicity, thus creating it tricky to explore and understand the chemistry of such material at the molecular level and device applications. Though diverse approaches [3] have been introduced to improve the dispersion of CNTs in different solvents including water, challenges still remain in developing simple, green, facile, and effective strategies for a large-scale production of CNT dispersions. To this end, in many studies a wide range of agents have been used. To give a few examples: solvents [4], biopolymers [5], and surfactants [6]. Meanwhile, when analyzing the scientific research articles published in various leading journals, regarding the dispersion of CNTs, it is really puzzling owing to the usage of different terminologies with respect to the dispersion of CNTs. Most of the studies indicated "dispersion"; however, considerable quantities of articles were published with the term "solubilization", which can be evidently seen from the literature analysis [7]. Hence, many researchers confound "dispersion" and "solubilization" and use the terms interchangeably, especially when describing the interaction of CNTs with solvents. Many scientists have mentioned that CNTs can be "solubilized in water or organic solvents" by means of polymers and/or surfactants, which is ambiguous. It is evident that there is, as a result of that, a lot of confusion regarding this fundamental matter. The basic and fundamental key question here is: are CNTs dissolved or dispersed in a liquid?Basically, "dispersion" and "solubilization" are different phenomena. Dispersion and solubilization can be defined as "a system, in which particles of any nature (e.g., solid, liquid, or gas) are dispersed in a continuous phase of a different composition (or state)" [8] and a "process, by which an agent increases the solubility or the rate of dissolution of a solid or liquid solute" [9], respectively. Hence, in general, the dispersion of solute particles in solvents leads to the formation of colloids or suspensions, and solutions may be obtained as a result of solubilization of solute molecules or ions in the specified solvent. Furthermore, dispersion is mostly related to solute particles, whereas solubility or solubilization is generally connected with solute molecules or ions.The main differences between a colloid and a solution are: A solution is homogenous and remains stable and does not separate after standing for any period of time. Further it cannot be separated by standard separation techniques such as filtration or centrifugation. A solution looks transparent and it can transmit the light. Also, solutions contain the solute in a size at the molecular or ionic level, typically less than 1 nm or maximum a few nm in all dimensions. A colloid is a mixture with particles sizes between 1 and 1000 nm in at least one dimension. It is opaque, non-transparent, and the particles are large enough to scatter light. Colloids are not as stable as solutions and the dispersed particles (comparatively larger-sized particles) may be conveniently separated by standard separation techniques such as (ultra)centrifugation or filtration. Frequently, dispersed particles in colloidal systems may slowly agglomerate owing to inter-particle attractions over prolonged periods of time and, as a result, colloidal dispersions may form flocs or flakes.As far as CNTs are concerned, even though the diameter of the tubes is in the nanometer range (approximately between 0.4 and 3 nm for single-walled carbon nanotubes, and 1.4 and 100 nm for multi-walled carbon nanotubes) [10], their length can be up to several micrometers to millimeters. Further, it is a well-known fact that CNTs are not equal in size with respect to both diameter and length. Hence, the result of dispersion techniques mostly used and adopted to produce well-dispersed CNTs in either aqueous and/or organic media are typically dispersions of differently sized tubes. Consequently, based on the definition [6,7] and the abovementioned points, the mixture of CNTs and water or organic solvents, whether in the presence or non-presence of dispersing agents such as surfactants or polymers, is just a colloidal dispersion and not a solution. Figure ​Figure11 shows the schematic illustration for the formation of dispersed CNTs in a liquid with the aid of a dispersing agent. Simultaneously, the dispersion can result in a debundling or individualization of the bundled CNTs.Open in a separate windowFigure 1Schematic showing the transition of the bundled to the individualized, dispersed state of carbon nanotubes in a liquid with the aid of a dispersing agent.Therefore, "solubilization" is a process to achieve a stable solution, whereas "dispersion" is a form of colloidal system. Here we conclude that the mixture obtained by using CNTs and a liquid medium (water or organic solvents) with or without surfactants or polymers is a dispersion of CNTs in the medium, but not a solution. Further, in our opinion, one cannot solubilize CNTs in water or organic solvents. Hence, we recommend to restrict the use of the term "solubilization" or "solution," instead we should use the term "dispersion" or "colloid," when dealing with CNTs. Further, we think that this should be also applicable for nanoparticles of comparable dimensions such as metal and metal oxide nanoparticles, polymer nanoparticles, etc., if the criteria of the definitions given above are fulfilled.In short, the term "dispersion" should exclusively be used as far as CNTs are concerned, and the use of the term "solution" should be avoided or restricted.     

Diffusion in porous silicon: effects on the reactivity of alkenes and electrochemistry of alkylated porous silicon

Alkenes are known to react with hydrogen-terminated silicon surfaces to produce robust organic monolayers that are attached to the surface via covalent SiC bonds. In this report we investigate the dependence of the rate of alkylation of porous silicon samples on the reaction time using photochemical initiation. The kinetics of the photochemical alkylation of hydrogen-terminated porous silicon by undec-1-ene in toluene were observed to be pseudo first order, however the apparent rate constant decreased as the concentration of undec-1-ene increased. This behaviour is opposite to what would be expected if the rate-limiting process was an elementary chemical reaction step involving the alkene. Instead, it suggests that transport of the alkene to reactive sites and in the correct orientation is the rate-limiting step. Comparison of the rates of alkylation of porous silicon by undec-1-ene and dimethoxytrityl (DMT)-undecenol is consistent with such an interpretation as the bulky DMT headgroup gives a lower rate of alkylation. The diffusion of some simple redox-active probe molecules in porous silicon was investigated using a scanning electrochemical microscope (SECM). The probe molecules are converted at diffusion-controlled rate at an inlaid disk ultramicroelectrode (UME) consisting of the cross-section of a microwire sealed in glass. If the microelectrode is placed a short distance above the porous silicon, the microelectrode current depends on kinetics of the electrochemical reactions at the porous silicon and the mass transport properties within the open thin layer cell formed by the microelectrode and the alkylated porous silicon. In order to differentiate the effects of finite heterogeneous kinetics at silicon from diffusion limitations, current-distance curves were fitted over a wide range of applied potentials (on the Si) and it was observed that the diffusion coefficient in the porous layer was strongly anisotropic. The measured diffusion rates are comparable to those in bulk water along the pores, but with negligible diffusion between pores. This indicates that few pore-pore interconnections exist in the porous silicon.     

Analytical estimate for curing‐induced stress and warpage in coating layers

A thermoset coating that is applied to an elastic substrate will develop residual stresses during curing because of polymerization shrinkage of the resin. This shrinkage only partly contributes to the residual stresses because, before gelation, the stresses relax completely. In this study, we developed explicit analytical expressions for the curing efficiency factor, the residual stresses, and the resulting warpage. We did this by assuming that after gelation, the material was in its rubbery state and that viscoelastic effects were absent. A difference between the free and constrained warpages during curing was made. The analytical warpage models were shown to give results comparable to those of the numerical calculations with a fully curing‐dependent viscoelastic material model. Furthermore, for the first time, accurate analytical expressions for the stress‐free temperature and stress‐free strain were obtained. With these expressions, the effect of curing shrinkage on the residual stresses could easily be incorporated into existing (numerical) stress analysis without the need for extensive curing‐dependent viscoelastic material models. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

A Potent Mimetic of the Siglec-8 Ligand 6’-Sulfo-Sialyl Lewisx

Siglecs are members of the immunoglobulin gene family containing sialic acid binding N-terminal domains. Among them, Siglec-8 is expressed on various cell types of the immune system such as eosinophils, mast cells and weakly on basophils. Cross-linking of Siglec-8 with monoclonal antibodies triggers apoptosis in eosinophils and inhibits degranulation of mast cells, making Siglec-8 a promising target for the treatment of eosinophil- and mast cell-associated diseases such as asthma. The tetrasaccharide 6’-sulfo-sialyl Lewis^x has been identified as a specific Siglec-8 ligand in glycan array screening. Here, we describe an extended study enlightening the pharmacophores of 6’-sulfo-sialyl Lewis^x and the successful development of a high-affinity mimetic. Retaining the neuraminic acid core, the introduction of a carbocyclic mimetic of the Gal moiety and a sulfonamide substituent in the 9-position gave a 20-fold improved binding affinity. Finally, the residence time, which usually is the Achilles tendon of carbohydrate/lectin interactions, could be improved.     

Differential Effects of Estrogen and Progestin on Apolipoprotein B100 and B48 Kinetics in Postmenopausal Women

The distinct effects of the estrogen and progestin components of hormonal therapy on the metabolism of apolipoprotein (apo) B‐containing lipoproteins have not been studied. We enrolled eight healthy postmenopausal women in a placebo‐controlled, randomized, double‐blind crossover study. Each subject received placebo, conjugated equine estrogen (CEE, 0.625 mg/day) and CEE plus medroxyprogesterone acetate (MPA, 2.5 mg/day) for 8 weeks in a randomized order, with a 4‐week washout between phases. Main outcomes were the fractional catabolic rate (FCR) and production rate (PR) of apo B100 in triglyceride‐rich lipoproteins (TRL), intermediate‐density lipoproteins (IDL) and low ‐density lipoprotein (LDL) and of apo B48 in TRL. Compared to placebo, CEE increased TRL apo B100 PR (p = 0.04). CEE also increased LDL apo B100 FCR (p = 0.02), but this effect was offset by a significant increase in LDL apo B100 PR (p = 0.04). Adding MPA to CEE negated the CEE effects resulting in no significant changes in TRL apo B100 PR and LDL apo B100 FCR and PR relative to placebo. Relative to placebo, during CEE there was a trend toward a reduction in plasma apo B48 concentrations and PR (p = 0.07 and p = 0.12, respectively). Compared with CEE, CEE + MPA significantly increased TRL apo B48 FCR (p = 0.02) as well as apo B48 PR (p = 0.01), resulting in no significant changes in apo B48 concentration. Estrogen and progestin have independent and opposing effects on the metabolism of the atherogenic apo B100‐ and apo B48‐containing lipoproteins.     

Acquired and Partially De Novo Synthesized Pyrrolizidine Alkaloids in Two Polyphagous Arctiids and the Alkaloid Profiles of Their Larval Food-Plants

The profiles of pyrrolizidine alkaloids (PAs) in the two highly polyphagous arctiids Estigmene acrea and Grammia geneura and their potential PA sources in southeastern Arizona were compiled. One of four species of Boraginaceae, Plagiobothrys arizonicus, contained PAs; this is the first PA record for this plant species. The principle PA sources are Senecio longilobus (Asteraceae) and Crotalaria pumila (Fabaceae). The known PA pattern of S. longilobus was extended; the species was found to contain six closely related PAs of the senecionine type. Three novel PAs of the monocrotaline type, named pumilines A-C, were isolated and characterized from C. pumila, a species not studied before. The pumilines are the major PAs in the seeds, while in the vegetative organs they are accompanied by the simple necine derivatives supinidine and as the dominant compound subulacine (1beta,2beta-epoxytrachelanthamidine). In both plant species, the PAs are stored as N-oxides, except C. pumila seeds, which accumulate the free bases. Great variation in PA composition was observed between local populations of C. pumila. The PA profiles were established for larvae and adults of E. acrea that as larvae had fed on an artificial diet supplemented with crotalaria-powder and of G. geneura fed with S. longilobus. In both experiments, the larvae had a free choice between the respective PA source and diet or food plants free of PAs. The profiles compiled for the two species reflect the alkaloid profiles of their PA sources with one exception, subulacine could never be detected in E. acrea. Besides acquired PAs, insect PAs synthesized from acquired necine bases and necic acids of insect origin were detected in the two arctiid species. These insect PAs that do not occur in the larval food sources accounted for some 40-70% (E. acrea) and 17-37% (G. geneura) of total PAs extracted from the insects. A number of novel insect PAs were identified. Plant-acquired and insect PAs were found to accumulate as N-oxides. The results are discussed in relation to specific biochemical, electrophysiological, and behavioral mechanisms involved in PA sequestration by arctiids.     

Desaturases fused to their electron donor

Fatty acid desaturations in the carboxy‐terminal segment from C1—C10 are catalyzed in many, but not in all cases, by desaturase enzymes which are fused to their electron donor cytochrome b₅. Several of these enzymes (“front‐end desaturases”) from a wide variety of organisms have been cloned and functionally expressed for proof of regio‐, stereo‐ and chain length‐selectivity. In most cases the actual status of the substrate chain, whether coenzyme A thioester or component of a membrane lipid, is not known. The cytochrome b₅ domain is located N‐terminally, internally or C‐terminally. Compared to the free cytochrome b₅ , the fused domains show a significant reduction of acidic amino acid residues on the surface of the four helices enclosing the heme group. It is discussed how this may contribute to hydrophobic domain pairing required for interdomain electron transport. This is in contrast to the mode of interaction of free cytochrome b₅ with its partners, which is governed by electrostatic charge pairing. A look at crystallized or computer‐simulated models involving fused or free cytochrome b₅ helps to outline the problems encountered by optimizing the docking of partners and the exchange of electrons between domains of different degrees of mobility.     

Improvement of Aglycone π-Stacking Yields Nanomolar to Sub-nanomolar FimH Antagonists

Antimicrobial resistance has become a serious concern for the treatment of urinary tract infections. In this context, an anti-adhesive approach targeting FimH, a bacterial lectin enabling the attachment of E. coli to host cells, has attracted considerable interest. FimH can adopt a low/medium-affinity state in the absence and a high-affinity state in the presence of shear forces. Until recently, mostly the high-affinity state has been investigated, despite the fact that a therapeutic antagonist should bind predominantly to the low-affinity state. In this communication, we demonstrate that fluorination of biphenyl α-d -mannosides leads to compounds with perfect π–π stacking interactions with the tyrosine gate of FimH, yielding low nanomolar to sub-nanomolar K_D values for the low- and high-affinity states, respectively. The face-to-face alignment of the perfluorinated biphenyl group of FimH ligands and Tyr48 was confirmed by crystal structures as well as ¹H,¹⁵N-HSQC NMR analysis. Finally, fluorination improves pharmacokinetic parameters predictive for oral availability.     

Nitrous oxide emissions from an Uruguayan argiudoll under different tillage and rotation treatments

Lack of local data limits estimation of nitrous oxide (N₂O) emissions from different land uses of Uruguay. As a first step towards obtaining local information, we measured from August 2003 to September 2004 N₂O fluxes from a rotation-by-tillage experiment established in 1993 and from a nearby natural pasture (NP). Nitrous oxide emission rates were measured on an event-driven basis by using the closed chamber technique with six replicates per treatment. Fluxes varied considerably with time and the higher rates (more than 30 g N ha⁻¹ day⁻¹) were generally associated with periods of high soil water content, high temperature, and/or decreasing soil nitrate. We could not identify, however, any statistically significant correlation between flux and these variables. Throughout the evaluation period, fluxes from crops or cultivated pastures tended to be higher than those from NP, but the effects of tillage (no-till and conventional tillage) or rotation (continuous tillage and rotation with pasture) were not consistent. The application of 112 kg N ha⁻¹ to barley did not increase N₂O fluxes probably due to a high fertilizer use efficiency caused by the recommended three-split application and by the lack of rain during this period. The annual cumulative flows of different treatments compared well with those estimated using IPCC methodology, but the high spatial and temporal variability observed in this one-year study indicate that further research is needed to obtain reliable data on N₂O fluxes from agricultural soils of Uruguay.