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Nicholas A Kotov

Publications and source records attributed to Nicholas A Kotov.

At least 19 recordsLinked to original sources
PubMed2006

Self-assembly of CdTe nanocrystals into free-floating sheets.

In their physical dimensions, surface chemistry, and degree of anisotropic interactions in solution, CdTe nanoparticles are similar to proteins. We experimentally observed their spontaneous, template-free organization into free-floating particulate sheets, which resemble the assembly of surface layer (S-layer) proteins. Computer simulation and concurrent experiments demonstrated that the dipole moment, small positive charge, and directional hydrophobic attraction are the driving forces for the self-organization process. The data presented here highlight the analogy of the solution behavior of the two vastly different classes of chemical structures.

Journal Article↗
PubMed2006

Fabry-Perot fringes and their application to study the film growth, chain rearrangement, and erosion of hydrogen-bonded PVPON/PAA films.

We observed Fabry-Perot fringes in the absorption spectra of hydrogen-bonded layer-by-layer (LBL) films of poly(vinyl pyrrolidone) (PVPON) and poly(acrylic acid) (PAA), which stem from the interferences between beams transmitted and partially reflected at the highly smooth film-air interface and film-quartz interface. The appearance and disappearance of Fabry-Perot fringes can be used to evaluate the homogeneity of the film. They also provide information about the film thickness. Using this optical phenomenon, with a minimal requirement of instrumentation, we studied the effect of several experimental conditions on the film buildup and structure. The film grows linearly with dipping cycles. Films fabricated from higher molecular weight polymers tend to be thicker. Increasing the concentration of the assembly solutions can also make thicker films. However, films from high molecular weight polymers or high concentration assembly solutions may be heterogeneous and do not display Fabry-Perot fringes in their absorption spectra. The defects in these heterogeneous films can be healed by a postannealing in water or diluted HCl to allow the chain rearrangement to complete. We further found the PVPON/PAA films can be eroded by long-term annealing in water or diluted HCl by monitoring the movement of the Fabry-Perot fringes. In most cases, the erosion rate is constant with annealing time. The erosion rate decreases with a decrease in the pH of the media and an increase in the molecular weight of the polymers.

Journal Article↗
PubMed2006

On the origin of a permanent dipole moment in nanocrystals with a cubic crystal lattice: effects of truncation, stabilizers, and medium for CdS tetrahedral homologues.

A large anomalous dipole moment has previously been reported for nanocrystals with a cubic crystal lattice. By considering truncations of a regular tetrahedral CdS nanocrystal, the hypothesis that shape asymmetry is responsible for the observed dipole moment was tested and verified. The location and degree of the truncations were systematically varied, and corresponding dipole moments were calculated by using a PM3 semiempirical quantum mechanical algorithm. The calculated dipole moment of 50-100 D is in good agreement with a variety of experimental data. This approach also affords simple evaluation of the potential effect of the media for aqueous dispersions of nanocrystals. The substitution of the truncated corner(s) by molecules of H2O typically results in a substantial increase of the dipole moment, and often, in the reversal of its direction. The molecular modeling approach presented here is suitable for detailed theoretical studies of the dipole moments of II-VI and other nanoparticles and interparticle interactions in fluids. The data obtained from these calculations can be the starting point for modeling of agglomeration and self-organization behavior of large nanoparticle ensembles.

Cadmium Compounds↗
PubMed2006

Spontaneous CdTe --> alloy --> CdS transition of stabilizer-depleted CdTe nanoparticles induced by EDTA.

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.

Alloys↗
PubMed2006

Spontaneous transformation of CdTe nanoparticles into angled Te nanocrystals: from particles and rods to checkmarks, X-marks, and other unusual shapes.

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.

Cadmium↗
PubMed2006

Monte carlo computer simulation of chain formation from nanoparticles.

Spontaneous assembly of long chains of nanoparticles (NPs) has been experimentally observed for many different materials including nanocolloids of semiconductors, metal oxides, and metals. While the origin of dipole moment in various colloids can be different, a universal explanation of chain assembly can be provided by the hypothesis of dipole-dipole attraction of nanocolloids. In this paper, we describe the application of the Monte Carlo method for modeling of self-organization of large ensembles of NPs. As the first approximation, the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory provides an adequate description of self-organization of several hundreds of NPs. Unlike microscale colloids that served as a classical model for DLVO, we used a distance-dependent media dielectric constant. The simulated chains are morphologically and geometrically similar to those observed experimentally. This establishes the fundamentally important ability of NPs to self-assemble due to their intrinsic anisotropy. Thermodynamic analysis of Monte Carlo results reveals the role of partial removal of the stabilizer shell in CdTe nanocolloids necessary for reduction of interparticle repulsion. Analysis of the field distribution around short chains demonstrates that the growth of linear agglomerates is kinetically controlled by a high activation barrier for NPs approaching from all of the directions except one end of the chain. The presented algorithm can be applied to other interparticle interactions, such as induced dipoles, which can stimulate chain formation in the absence of permanent dipole moment. It can also serve as a theoretical foundation for the understanding of the large complex superstructures forming from anisotropic and anisometric NPs. Monte Carlo simulation of nanoscale dipoles can also be extended to the interactions of NP with proteins, and related biological systems important for a variety of applications in medicine.

Journal Article↗
PubMed2006

CNT-CdTe versatile donor-acceptor nanohybrids.

Single wall carbon nanotubes (SWNT) and multiwall carbon nanotubes (MWNT) were linked to thioglycolic acid (TGA)-capped CdTe nanoparticles (NP) through electrostatic interactions producing photoactive superstructures. The novel nanohybrids were characterized both in the ground and excited states with specific accent on electron-transfer chemistry. In fact, both assays provide kinetic and spectroscopic evidence that support a partial transfer of charge density, with rapid formation of microsecond-lived radical ion pair states. Since nanotubes provide a quick transportation route of charge carriers to the electrode, we took this remarkable finding further and constructed photoelectrochemical cells. Photocurrents were generated through the implementation of CdTe and SWNT or MWNT, which serve as excited-state electron donor components and electron acceptors, respectively.

Journal Article↗
PubMed2006

Structural diversity in binary nanoparticle superlattices.

Assembly of small building blocks such as atoms, molecules and nanoparticles into macroscopic structures--that is, 'bottom up' assembly--is a theme that runs through chemistry, biology and material science. Bacteria, macromolecules and nanoparticles can self-assemble, generating ordered structures with a precision that challenges current lithographic techniques. The assembly of nanoparticles of two different materials into a binary nanoparticle superlattice (BNSL) can provide a general and inexpensive path to a large variety of materials (metamaterials) with precisely controlled chemical composition and tight placement of the components. Maximization of the nanoparticle packing density has been proposed as the driving force for BNSL formation, and only a few BNSL structures have been predicted to be thermodynamically stable. Recently, colloidal crystals with micrometre-scale lattice spacings have been grown from oppositely charged polymethyl methacrylate spheres. Here we demonstrate formation of more than 15 different BNSL structures, using combinations of semiconducting, metallic and magnetic nanoparticle building blocks. At least ten of these colloidal crystalline structures have not been reported previously. We demonstrate that electrical charges on sterically stabilized nanoparticles determine BNSL stoichiometry; additional contributions from entropic, van der Waals, steric and dipolar forces stabilize the variety of BNSL structures.

Journal Article↗
PubMed2005

Layer-by-layer assembly of nacre-like nanostructured composites with antimicrobial properties.

In a recent report, we have presented the layer-by-layer (LBL) assembly of a biomimetic nanostructured composite from Na(+)-montmorillonite clay nanosheets and poly(diallylmethylammonium chloride) (Tang, Z.; Kotov, N.; Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413). The structure, deformation mechanism, and mechanical properties of the material are very similar to those of natural nacre and lamellar bones. This fact prompts further investigation of these composites as potential bone implants. LBL assembly affords preparation of multifunctional composites, and here we demonstrate that not only mechanical strength, but also antibacterial activity, can be introduced in these implantable materials by alternating clay layers with starch-stabilized silver nanoparticles. The resulting composite showed excellent structural stability with no detectable levels of silver lost over a 1 month period. Evaluation of the antibacterial properties showed almost complete growth inhibition of E. coli over an 18 h period. The amount of silver eluted from the LBL composite over a 1 month period was determined to be only 0.5-3.0 microg/L. This concentration of silver did not prevent the growth of the mammalian tissue cultures. The LBL composite has shown biocompatibility with the human osteoblast cell line.

Animals↗
PubMed2005

Single-walled carbon nanotube combing during layer-by-layer assembly: from random adsorption to aligned composites.

Oriented SWNTs in polymer composites have shown dramatic improvements in the physical properties of a composite because of the anisotropic shape and properties of SWNTs. Controlled alignment of SWNTs during composite fabrication implies better material function performance. This letter reports a new fabrication technique whereby aligned SWNTs and robust SWNT-polymer composites can be made using a fusion method of SWNT combing and layer-by-layer (LBL) assembly. As we previously reported, LBL assembly demonstrated exceptional processing ability in constructing the uniform distribution of a SWNT-polymer composite. Combined with this uniformity, this SWNT combing technique endows controlled alignment of single-stranded SWNTs in a SWNT-polymer composite system. SWNT combing employs air-water interfacial forces to change the molecular topography from the random adsorption state to the stretched alignment of SWNTs. More specifically, air-water interfacial forces are associated with an excess viscous drag force and an intrinsic dewetting rate along SWNTs. Moreover, the alignment efficiency of SWNTs is high enough to construct a multilayered LBL film with horizontal-linear weaving structures. This simple method also can be applied for aligning other nanowire materials because it utilizes simple geometric features of SWNTs.

Journal Article↗
PubMed2005

What is the effective charge of TGA-stabilized CdTe nanocolloids?

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.

Journal Article↗
PubMed2005

Aqueous dispersions of single-wall and multiwall carbon nanotubes with designed amphiphilic polycations.

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.

Light↗
PubMed2005

Cell distribution profiles in three-dimensional scaffolds with inverted-colloidal-crystal geometry: modeling and experimental investigations.

Limited ingrowth of stromal cells is observed when a three-dimensionally ordered scaffold possessing inverted-colloidal-crystal geometry is used to culture adherent cells. In this work, a computational model explaining, as well as predicting, experimental cell distributions is developed. It incorporates a modified Contois cell-growth model that includes the effects of nutrient saturation, competitive product inhibition, and cell-contact inhibition to describe the scaffold-cell system. Our results agree with the hypothesis that the rapid growth of cells on the surface of the scaffold depletes the nutrient supply to the core, resulting in the preferential growth on the exterior of the scaffold. When the cells are cultured in a scaffold subjected to a uniform velocity field, they penetrate to a greater extent into the scaffold core. Alternative seeding and culture strategies are suggested and evaluated.

Biocompatible Materials↗
PubMed2005

Biological assembly of nanocircuit prototypes from protein-modified CdTe nanowires.

CdTe nanowires made by self-organization of CdTe nanoparticles in aqueous media were separately conjugated with complementary biological connectors, such as antigen-antibody and biotin-streptavidin. Transmission electron microscopy images and Forster resonance energy transfer measurements in nanowire superstructures with different diameters indicate that biological affinity of the attached proteins results in the formation of crossbar and end-to-side connections between the nanowires. A prototype of a logical circuit made from a triangular arrangement of the nanowires spontaneously assembled on a Si substrate was examined by conducting atomic force microscopy. While diode-like behavior was observed in the sides of the triangle, the nanowire junction points were found to be nonconductive. It was attributed to high tunneling barrier created by protein molecules wedged between the nanowires. Suggestions are made how to reduce it or use the insulating gap between the nanowires as a framework for single-electron devices.

Antigen-Antibody Complex↗
PubMed2005

Bioconjugated superstructures of CdTe nanowires and nanoparticles: multistep cascade Förster resonance energy transfer and energy channeling.

Nanoparticle/nanowire assemblies with a degree of radial organization were prepared around luminescent semiconducting CdTe nanowires using bioconjugation with streptavidin and D-biotin linkers. Red-emitting nanowires (6.62 +/- 1.55 nm diameter, 512 +/- 119 nm length) and green-emitting nanoparticles (3.2 +/- 0.7 nm diameter) were surface-modified with biotin, while orange-emitting nanoparticles (4.1 +/- 1.2 nm diameter) were decorated with streptavidin. CdTe nanocrystals produced two fuzzy layers around the nanowires in which the diameter of CdTe nanoparticles decreased with the distance from the nanowire axis. Förster resonance energy transfer (FRET) from the outside layer of nanoparticles to the central nanowire was observed for nanowires conjugated with 4.1 nm CdTe. Addition of 3.2 nm CdTe resulted in a red-orange-green optical progression with band gaps of CdTe decreasing toward the axis of the superstructure. In this case, 4-fold luminescence enhancement of the nanowire luminescence was observed and was attributed to multistep FRET. This observation indicated the accumulation of photogenerated excitons in the cascade terminal. A simple model of multiconjugated superstructure with cascade energy transfer is developed and used to describe and understand the experimental data. The experimental data and theoretical model suggest the possibility of utilization of the prepared superstructures with radial symmetry in several classes of optoelectronic devices including nanomaterials for energy collection. They can also be a convenient model object for the investigation of methods of energy funneling in nanoscale assemblies.

Biotin↗