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Chemical, physical, biological and materials engineering disciplines use a variety of chiroptical spectroscopies to probe geometrical and optical asymmetry in molecules and particles. Electronic (ECD) and vibrational (VCD) circular dichroism are the most common of these techniques and collectively enable the studies of electronic and vibronic transitions with energies between 0.1 and 5.0 eV. The vibrational states with characteristic energies in the range of 0.001-0.01 eV carry valuable information about concerted intermolecular motions in molecules and crystals involving multiple atoms. These vibronic transitions located in the terahertz (THz) part of the spectrum become increasingly more important for the chemistry, physics, and biology of complex molecules and materials However, the methodology and hardware of THz circular dichroism (TCD) are much less developed than the chiroptical spectroscopies for ultraviolet, visible, near- and mid infrared photons. Here we provide theoretical foundations, practical implementations, comparative assessments, and exemplary applications of TCD spectroscopy. We show that the sign, intensity, and position of TCD peaks are highly sensitive to the three-dimensional structure and long-range organization of molecular crystals, which offer unique capabilities to study (bio) molecules, their crystals, and nanoscale assemblies and apply the novel data processing methodologies. TCD also offers a convenient toolbox to identify new physical phenomena, such as chiral phonons and their propagation in nanostructured matter. We also discuss the major challenges, emerging opportunities and promising research directions, including broad investigation of chiral phonons observed in chiral (nano) crystals and emerging machine learning methodologies for TCD in biological and nanoscale structures. Ubiquity of low-frequency vibrations with rotational components in biomolecular structures, combined with sharpness of peaks in TCD spectra, enables a variety of technological translations.

The effect of chemical-composition modification on the chiroptical property of chiral organic ammonium cation-containing organic inorganic hybrid perovskite (chiral OIHP) is investigated. Varying the mixing ratio of bromide and iodide anions in S- or R-C6H5CH2(CH3)NH3)2PbI4(1-x)Br4x modifies the band gap of chiral OIHP, leading to a shift of the circular dichroism (CD) signal from 495 to 474 nm. However, it is also found that an abrupt crystalline structure transition occurs, and the CD signal is turned off when iodide-determinant phases are transformed into the bromide-determinant phase. To obtain CD in the wavelength range where the bromide-determinant phase is supposed to exhibit chiroptical activity, that is

A variety of inorganic nanoscale materials produce microscale particles with highly corrugated geometries, but the mechanism of their formation remains unknown. Here we found that uniformly sized CdS-based hedgehog particles (HPs) self-assemble from polydisperse nanoparticles (NPs) with diameters of 1.0-4.0 nm. The typical diameters of HPs and spikes are 1770 ± 180 and 28 ± 3 nm, respectively. Depending on the temperature, solvent, and reaction times, the NPs self-assemble into nanorods, nanorod aggregates, low-corrugation particles, and other HP-related particles with complexity indexes ranging from 0 to 23.7. We show that "hedgehog", other geometries, and topologies of highly corrugated particles originate from the thermodynamic preference of polydisperse NPs to attach to the growing nanoscale cluster when electrostatic repulsion competes with van der Waals attraction. Theoretical models and simulations of the self-assembly accounting for the competition of attractive and repulsive interactions in electrolytes accurately describe particle morphology, growth stages, and the spectrum of observed products. When kinetic parameters are included in the models, the formation of corrugated particles with surfaces decorated by nanosheets, known as flower-like particles, were theoretically predicted and experimentally observed. The generality of the proposed mechanism was demonstrated for the formation of mixed HPs via a combination of CdS and Co3O4 NPs. With unusually high dispersion stability of HPs in unfavorable solvents including liquid CO2, mechanistic insights into HP formation are essential for their structural adaptation for applications from energy storage, catalysis, water treatment, and others.

Hedgehog particles (HPs) replicating the spiky geometry of pollen grains revealed surprisingly high dispersion stability regardless of whether their hydrophobicity/hydrophilicity matches that of the media or not. This property designated as omnidispersibility is attributed to the drastic reduction of van der Waals interactions between particles coated with stiff nanoscale spikes as compared to particles of the same dimensions with smooth surfaces. One may hypothesize but it remains unknown, however, whether HPs modified with polymers or nanoparticles (NPs) would retain this property. Surface modifications of the spikes will expand the functionalities of HPs, making possible their utilization as omnidispersible carriers. Here, we show that HPs carrying dense conformal coatings made by layer-by-layer (LBL/LbL) assembly maintain dispersion stability in environments of extreme polarity and ionic strength. HPs, surface-modified by multilayers of polymers and gold NPs, are capable of surface-enhanced Raman scattering (SERS) and overcome the limited colloidal stability of other SERS probes. The agglomeration resilience of HPs leads to a greater than one order of magnitude increase of SERS intensity as compared to colloids with smooth surfaces and enables simultaneous detection of several targets in complex media with high ionic strength. Omnidispersible optically active colloids open the door for rapid multiplexed SERS analysis in biological fluids and other applications.

Chiral self-assembled nanomaterials with biological applications have attracted great interest. In this study, DNA-driven gold-upconversion nanoparticle (Au-UCNP) pyramids were fabricated to detect intracellular microRNA (miRNA) in real time. The Au-UCNP pyramids are doubly optically active, displaying strong plasmonic circular dichroism (CD) at 521 nm and significant luminescence in 500-600 nm, and therefore can be monitored by both of them. CD will decrease while the luminescence intensity increases in the presence of miRNA. The experimental results show that the CD intensity had an outstanding linear range from 0.073 to 43.65 fmol/10 μg(RNA) and a limit of detection (LOD) of 0.03 fmol/10 μg(RNA), whereas the luminescence intensity ranged from 0.16 to 43.65 fmol/10 μg(RNA) with a LOD of 0.12 fmol/10 μg(RNA). These data indicate that the CD signal is much more sensitive to the concentration of miRNA than the luminescent signal, which is attributed to the strong CD intensity arising from the spin angular momentum of the photon interaction with chiral nanostructures and the plasmonic enhancement of the intrinsic chirality of DNA molecules in the pyramids. This approach opens up a new avenue to the ultrasensitive detection and quantification of miRNA in living cells.

We report the synthesis and characterization of a chiral, shape-persistent, perylene-diimide-based nanoribbon. Specifically, the fusion of three perylene-diimide monomers with intervening naphthalene subunits resulted in a helical superstructure with two [6]helicene subcomponents. This π-helix-of-helicenes exhibits very intense electronic circular dichroism, including one of the largest Cotton effects ever observed in the visible range. It also displays more than an order of magnitude increase in circular dichroism for select wavelengths relative to its smaller homologue. These impressive chiroptical properties underscore the potential of this new nanoribbon architecture in the context of chiral electronic materials.

The ability of semiconductor nanoparticles (NPs) to self-assemble has been known for several decades. However, the limits of the geometrical and functional complexity for the self-assembled nanostructures made from simple often polydispersed NPs are still continuing to amaze researchers. We report here the self-assembly of primary ∼2–4 nm FeSe2 NPs with puck-like shapes into either (a) monocrystalline nanosheets ∼5.5 nm thick and ∼1000 nm in lateral dimensions or (b) mesoscale hedgehogs ∼550 nm in diameter with spikes of ∼250 nm in length, and ∼10–15 nm in diameter, the path of the assembly is determined by the concentration of dodecanethiol (DT) in the reaction media. The nanosheets represent the constitutive part of hedgehogs. They are rolled into scrolls and assembled around a single core with distinct radial orientation forming nanoscale “needles” approximately doubling its fractal dimension of these objects. The core is assembled from primary NPs and nanoribbons. The size distribution of the mesoscal...

The chirality of nanoparticles (NPs) and their assemblies has been investigated predominantly for noble metals and II-VI semiconductors. However, ceramic NPs represent the majority of nanoscale materials in nature. The robustness and other innate properties of ceramics offer technological opportunities in catalysis, biomedical sciences, and optics. Here we report the preparation of chiral ceramic NPs, as represented by tungsten oxide hydrate, WO3-x·H2O, dispersed in ethanol. The chirality of the metal oxide core, with an average size of ca. 1.6 nm, is imparted by proline (Pro) and aspartic acid (Asp) ligands via bio-to-nano chirality transfer. The amino acids are attached to the NP surface through C-O-W linkages formed from dissociated carboxyl groups and through amino groups weakly coordinated to the NP surface. Surprisingly, the dominant circular dichroism bands for NPs coated by Pro and Asp are different despite the similarity in the geometry of the NPs; they are positioned at 400-700 nm and 500-1100 nm for Pro- and Asp-modified NPs, respectively. The differences in the spectral positions of the main chiroptical band for the two types of NPs are associated with the molecular binding of the two amino acids to the NP surface; Asp has one additional C-O-W linkage compared to Pro, resulting in stronger distortion of the inorganic crystal lattice and greater intensity of CD bands associated with the chirality of the inorganic core. The chirality of WO3-x·H2O atomic structure is confirmed by atomistic molecular dynamics simulations. The proximity of the amino acids to the mineral surface is associated with the catalytic abilities of WO3-x·H2O NPs. We found that NPs facilitate formation of peptide bonds, leading to Asp-Asp and Asp-Pro dipeptides. The chiroptical activity, chemical reactivity, and biocompatibility of tungsten oxide create a unique combination of properties relevant to chiral optics, chemical technologies, and biomedicine.

Iron chalcogenides hold considerable promise for energy conversion and biomedical applications. Realization of this promise has been hindered by the lack of control over the crystallinity and nanoscale organization of iron chalcogenide films. High-quality nanoparticles (NPs) from these semiconductors will afford further studies of photophysical processes in them. Phase-pure NPs from these semiconductors can also serve as building blocks for mesoscale iron chalcogenide assemblies. Herein we report a synthetic method for FeSe(x) (x = 1, 2) NPs with a diameter of ca. 30 nm that satisfy these needs. The high crystallinity of the individual NPs was confirmed by transmission electron microscopy (TEM) and energy-dispersive X-ray analysis. TEM tomography images suggest pucklike NP shapes that can be rationalized by bond relaxation at the NP edges, as demonstrated in large-scale atomic models. The prepared FeSe(x) NPs display strong photoluminescence with a quantum yield of 20%, which was previously unattainable for iron chalcogenides. Moreover, they also show strong off-resonant luminescence due to two-photon absorption, which should be valuable for biological applications.

Chirality at the nanometer scale represents one of the most rapidly developing areas of research. Self-assembly of DNA-nanoparticle (NP) hybrids enables geometrically precise assembly of chiral isomers. The concept of a discrete chiral nanostructure of tetrahedral shape and topology fabricated from four different NPs located in the corners of the pyramid is fundamental to the field. While the first observations of optical activity of mixed pyramidal assemblies were made in 2009 (Chen, W.; Nano Lett. 2009, 9, 2153-2159), further studies are difficult without finely resolved optical data for precisely organized NP pyramidal enantiomers. Here we describe the preparation of a family of self-assembled chiral pyramids made from multiple metal and/or semiconductor NPs with a yield as high as 80%. Purposefully made R- and S-enantiomers of chiral pyramids with four different NPs from three different materials displayed strong chiroptical activity, with anisotropy g-factors as high as 1.9 × 10(-2) in the visible spectral range. Importantly, all NP constituents contribute to the chiroptical activity of the R/S pyramids. We were able to observe three different circular dichroism signals in the range of 350-550 nm simultaneously. They correspond to the plasmonic oscillations of gold, silver, and bandgap transitions of quantum dots. Tunability of chiroptical bands related to these transitions is essential from fundamental and practical points of view. The predictability of optical properties of pyramids, the simplicity of their self-assembly in comparison with lithography, and the possibility for polymerase chain reaction-based automation of their synthesis are expected to facilitate their future applications.

Detailed understanding of the mechanism of dielectrophoresis (DEP) and the drastic improvement of its efficiency for small size-quantized nanoparticles (NPs) open the door for the convergence of microscale and nanoscale technologies. It is hindered, however, by the severe reduction of DEP force in particles with volumes below a few hundred cubic nanometers. We report here DEP assembly of size-quantized CdTe nanoparticles (NPs) with a diameter of 4.2 nm under AC voltage of 4–10 V. Calculations of the nominal DEP force for these NPs indicate that it is several orders of magnitude smaller than the force of the Brownian motion destroying the assemblies even for the maximum applied AC voltage. Despite this, very efficient formation of NP bridges between electrodes separated by a gap of 2 μm was observed even for AC voltages of 6 V and highly diluted NP dispersions. The resolution of this conundrum was found in the intrinsic ability of CdTe NPs to self-assemble. The species being assembled by DEP are substantia...

Single-walled carbon nanotube (SWNT) and other carbon-based coatings are being considered as replacements for indium tin oxide (ITO). The problems of transparent conductors (TCs) coatings from SWNT and similar materials include poor mechanical properties, high roughness, low temperature resilience, and fast loss of conductivity. The simultaneous realization of these desirable characteristics can be achieved using high structural control of layer-by-layer (LBL) deposition, which is demonstrated by the assembly of hydroethyl cellulose (HOCS) and sulfonated polyetheretherketone (SPEEK)-SWNTs. A new type of SWNT doping based on electron transfer from valence bands of nanotubes to unoccupied levels of SPEEK through π-π interactions was identified for this system. It leads to a conductivity of 1.1 × 10(5) S/m at 66 wt % loadings of SWNT. This is better than other polymer/SWNT composites and translates into surface conductivity of 920 Ω/◻ and transmittance of 86.7% at 550 nm. The prepared LBL films also revealed unusually high temperature resilience up to 500 °C, and low roughness of 3.5 nm (ITO glass -2.4 nm). Tensile modulus, ultimate strength, and toughness of such coatings are 13 ± 2 GPa, 366 ± 35 MPa, and 8 ± 3 kJ/m(3), respectively, and exceed corresponding parameters of all similar TCs. The cumulative figure of merit, ∏(TC), which included the critical failure strain relevant for flexible electronics, was ∏(TC) = 0.022 and should be compared to ∏(TC) = 0.006 for commercial ITO. Further optimization is possible using stratified nanoscale coatings and improved doping from the macromolecular LBL components.

It is observed in this study that the chirality of cysteine stabilizers has a distinct effect on both the growth kinetics and the optical properties of CdTe nanocrystals synthesized in aqueous solution. The effect was studied by circular dichroism spectroscopy, temporal UV-vis spectroscopy, photoluminescence spectroscopy, and several other microscopy and spectroscopic techniques including atomic modeling. Detailed analysis of the entirety of experimental and theoretical data led to the hypothesis that the atomic origin of chiral sites in nanocrystals is topologically similar to that in organic compounds. Since atoms in CdTe nanocrystals are arranged as tetrahedrons, chirality can occur when all four atomic positions have chemical differences. This can happen in apexes of nanocrystals, which are the most susceptible to chemical modification and substitution. Quantum mechanical calculations reveal that the thermodynamically preferred configuration of CdTe nanocrystals is S type when the stabilizer is D-cysteine and R type when L-cysteine is used as a stabilizer, which correlates well with the experimental kinetics of particle growth. These findings help clarify the nature of chirality in inorganic nanomaterials, the methods of selective production of optical isomers of nanocrystals, the influence of chiral biomolecules on the nanoscale crystallization, and practical perspectives of chiral nanomaterials for optics and medicine.

ZnO hexagonal pyramids were obtained in hydrophilic media without any traditional stabilizers (capping agents). The absence of a thick organic shell reducing the anisotropy of nanoparticle (NP) interactions, oxide nature of the materials, and new geometry of the nanocrystals makes possible the observation of new self-organization phenomena. Several new features not present in the previous cases of NP self-organization were identified and discussed. The formation of ZnO pyramids involved recrystallization of larger amorphous NPs followed by the multistage disassembly of intermediate aggregates into individual virtually perfectly shaped nanocrystals. The evolution of NPs begins with crystallization of clustered plates within the original amorphous spherical colloids, and then agglomerated truncated pyramids are formed. These agglomerates further transform into chained pyramids, which eventually separate from each other. The crystallization and disassembly processes can be associated with the decrease of potential and anisotropy of the attractive force field around the crystallites represented in part by dipole moments. The reassembly of the pyramids can still be attained via engaging excluded volume interaction after adding similarly charged polymer. Overall, in this system, we see the first examples of (1) coupled crystallization and disassembly process; (2) induced assembly of nanoscale particles using excluded volume interactions, which were previously used only for aggregation of microscale colloids; and (3) nanoparticle assemblies with variable and experimentally verifiable relative orientation of dipoles including head-to-tail, tail-to-tail pairs, and antiparallel chains. Described assemblies of ZnO pyramids with collective behavior of individual building blocks as well as distinct and experimentally controlled stages of assembly and disassembly present a fundamentally interesting nanoparticle system with rich dynamic behavior.

CdTe nanoparticles stabilized by l-cysteine are chemically transformed into CdS nanoparticles of the same diameter via an intermediate CdTeS alloy without any auxiliary source of sulfur. The reaction is induced by ethylenediaminetetraacetic acid dipotassium salt dehydrate (EDTA), which was demonstrated experimentally to act as a catalyst by partially removing thiol stabilizers from the nanoparticle surface. It is hypothesized that addition of EDTA facilitates Te(2-) release, and oxidation of Te(2-) drives the nanoparticle transition process. Unlike many reports on reactions catalyzed by nanocolloids, this is likely to be the first observation of a catalytic reaction in which nanoparticles function as a substrate rather than a catalyst. It opens new pathways for the synthesis of novel nanoscale II-VI and other semiconductors and represents an interesting case of chemical processes in nanocolloids with reactivity increased by depletion of the surface layer of thiol stabilizers. This includes but is not limited to accurate control over the particle composition and crystallization rate. The slow rate of the CdTe --alloy --CdS transition is important for minimizing defects in the crystal lattice and results in a substantial increase of the quantum yield of photoluminescence over the course of the transition.

Poor solubility of single-walled and multiwalled carbon nanotubes (NTs) in water and organic solvents presents a considerable challenge for their purification and applications. Macromolecules can be convenient solubilizing agents for NTs and a structural element of composite materials for them. Several block copolymers with different chemical functionalities of the side groups were tested for the preparation of aqueous NT dispersions. Poly(N-cetyl-4-vinylpyridinium bromide-co-N-ethyl-4-vinylpyridinium bromide-co-4-vinylpyridine) was found to form exceptionally stable NT dispersions. It is suggested that the efficiency of macromolecular dispersion agents for NT solubilization correlates with the topological and electronic similarity of polymer-NT and NT-NT interactions in the nanotube bundles. Raman spectroscopy and atomic force and transmission electron microcopies data indicate that the polycations are wrapped around NTs forming a uniform coating 1.0-1.5 nm thick. The ability to wind around the NT originates in the hydrophobic attraction of the polymer backbone to the graphene surface and topological matching. Tetraalkylammonium functional groups in the side chains of the macromolecule create a cloud of positive charge around NTs, which makes them hydrophilic. The prepared dispersions could facilitate the processing of the nanotubes into composites with high nanotube loading for electronic materials and sensing. Positive charge on their surface is particularly important for biological and biomedical applications because it strengthens interactions with negatively charged cell membranes. A high degree of spontaneous bundle separation afforded by the polymer coating can also be beneficial for NT sorting.

The structure of the multilayer assemblies of yttrium iron garnet nanoparticles (YIG) with polyelectrolytes was investigated with the emphasis on the control of the particle density in the adsorption layers. It was found that the growth of YIG films prepared by the layer-by-layer assembly can occur via two deposition modes: (1) sequential adsorption of densely packed adsorption layers (normal growth mode) and (2) in-plane growth of isolated particle domains (lateral expansion mode). Importantly, the dependence of the optical density on the number of deposition cycles remains linear in both cases. Microscopy results indicate that the origin of the lateral growth is in the interplay of particle/particle and particle/polyelectrolyte interactions rather than in a substrate effect. The lateral expansion mode is a general attribute of the layer-by-layer deposition and can be observed for various aqueous colloids. For the preparation of sophisticated multifunctional assemblies on nanoparticles, the film growth via domain expansion should be avoided, and therefore, one must be able to control the growth pattern. The switch from lateral to normal growth mode can be effected by grafting charged organic groups to YIG nanoparticles. Hydrophobic interactions between the hydrocarbon groups of the modified YIG and polyelectrolyte significantly increase the attractive component of the particle/polyelectrolyte and particle/particle interactions. The films from modified YIG display densely packed nanoparticle layers with a greatly reduced number of defects.

Multiple properties of plasmonic assemblies are determined by their geometrical organization. While high degree of complexity was achieved for plasmonic superstructures based on nanoparticles (NPs), little is known about the stable and structurally reproducible plasmonic assemblies made up from geometrically diverse plasmonic building blocks. Among other possibilities, they open the door for the preparation of regiospecific isomers of nanoscale assemblies significant both from a fundamental point of view and optical applications. Here, we present a synthetic method for complex assemblies from NPs and nanorods (NRs) based on selective modification of NRs with DNA oligomers. Three types of assemblies denoted as End, Side, and Satellite isomers that display distinct elements of regiospecificity were prepared with the yield exceeding 85%. Multiple experimental methods independently verify various structural features, uniformity, and stability of the prepared assemblies. The presence of interparticle gaps with finely controlled geometrical parameters and inherently small size comparable with those of cellular organelles fomented their study as intracellular probes. Against initial expectations, SERS intensity for End, Side, and Satellite isomers was found to be dependent primarily on the number of the NPs in the superstructures rationalized with the help of electrical field simulations. Incubation of the label-free NP-NR assemblies with HeLa cells indicated sufficient field enhancement to detect structural lipids of mitochondria and potentially small metabolites. This provided the first proof-of-concept data for the possibility of real-time probing of the local organelle environment in live cells. Further studies should include structural optimization of the assemblies for multitarget monitoring of metabolic activity and further increase in complexity for applications in transformative optics.

Layer-by-layer assembly (LBL) can create advanced composites with exceptional properties unavailable by other means, but the laborious deposition process and multiple dipping cycles hamper their utilization in microtechnologies and electronics. Multiple rinse steps provide both structural control and thermodynamic stability to LBL multilayers, but they significantly limit their practical applications and contribute significantly to the processing time and waste. Here we demonstrate that by employing inkjet technology one can deliver the necessary quantities of LBL components required for film buildup without excess, eliminating the need for repetitive rinsing steps. This feature differentiates this approach from all other recognized LBL modalities. Using a model system of negatively charged gold nanoparticles and positively charged poly(diallyldimethylammonium) chloride, the material stability, nanoscale control over thickness, and particle coverage offered by the inkjet LBL technique are shown to be equal or better than the case of multilayers made with traditional dipping cycles. The opportunity for fast deposition of complex metallic patterns using a simple inkjet printer is also shown. The additive nature of LBL deposition based on the formation of insoluble nanoparticle-polyelectrolyte complexes of various compositions provides an excellent opportunity for versatile, multicomponent, and noncontact patterning for the simple production of stratified patterns that are much needed in advanced devices.

CdTe nanoparticles spontaneously transform into the branched Te nanocrystals with the unique, highly anisotropic shape of checkmarks after partial removal of the stabilizers of L-cysteine. The Te checkmarks are made in a relatively high yield and uniformity; the length of the arms is ca. 150 nm, whereas the angle between the arms is 74 degrees . Subsequent growth of the particle yields mothlike nanocrystals retaining geometrical anisotropy. Unlike the previous synthesis methods of branched nanocrystals, they are formed via a merger of individual rod-shaped crystallites. High-energy crystal faces on their apexes act as the sticky points causing the particles to join in the ends. This is the first demonstration of spontaneous transformation of binary semiconductor particles into highly anisotropic nanocolloids in an angled conformation. The end reactivity of starting Te rods can be used both for bottom-up fabrication of nanoscale electronics and relatively safe and nontoxic method of synthesis of Te-based optical and other materials.

The surface charge of semiconductor nanoparticles, Q, is an important parameter which determines their electrokinetic behavior, stability in water and polar solvents, functions of optical and electronic devices, self-assembly properties, and interactions with cell membranes. We have developed a simple method for quantitative determination of Q in their native aqueous environment. The method does not require the knowledge of exact atomic structure or make assumptions about effects of drying on charge distribution. The method is based on titration of nanoparticle dispersion with a solution of oppositely charged polyelectrolyte. The point of complete neutralization is recognized as an inflection point on the dependence of fluorescence intensity on the amount of polyelectrolyte added. Thioglycolic acid-stabilized CdTe nanoparticles 2 nm in diameter were found to carry an average Q from -2.6 to -5.5 for pH 7.5 to 10, respectively. This charge is found to be smaller than that calculated theoretically for an analogous structure (i.e., Q = -8), presumably due to adsorption of Cd(2+) ions on the stabilizer shell and on Te atoms with unsaturated valence located on the side planes of CdTe tetrahedrons.

Poor solubility of single-walled and multiwalled carbon nanotubes (NTs) in water and organic solvents presents a considerable challenge for their purification and applications. Macromolecules can be convenient solubilizing agents for NTs and a structural element of composite materials for them. Several block copolymers with different chemical functionalities of the side groups were tested for the preparation of aqueous NT dispersions. Poly(N-cetyl-4-vinylpyridinium bromide-co-N-ethyl-4-vinylpyridinium bromide-co-4-vinylpyridine) was found to form exceptionally stable NT dispersions. It is suggested that the efficiency of macromolecular dispersion agents for NT solubilization correlates with the topological and electronic similarity of polymer-NT and NT-NT interactions in the nanotube bundles. Raman spectroscopy and atomic force and transmission electron microcopies data indicate that the polycations are wrapped around NTs forming a uniform coating 1.0-1.5 nm thick. The ability to wind around the NT originates in the hydrophobic attraction of the polymer backbone to the graphene surface and topological matching. Tetraalkylammonium functional groups in the side chains of the macromolecule create a cloud of positive charge around NTs, which makes them hydrophilic. The prepared dispersions could facilitate the processing of the nanotubes into composites with high nanotube loading for electronic materials and sensing. Positive charge on their surface is particularly important for biological and biomedical applications because it strengthens interactions with negatively charged cell membranes. A high degree of spontaneous bundle separation afforded by the polymer coating can also be beneficial for NT sorting.

Novel organic (positively charged fullerene)−inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor−acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states.