Clearance properties of nano-sized particles and molecules as imaging agents: considerations and caveats.

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

and Applications of Fullerenes, Carbon Dots, Nanotubes, Graphene, Nanodiamonds, and Combined Superstructures Vasilios Georgakilas,† Jason A. Perman,‡ Jiri Tucek,‡ and Radek Zboril*,‡ †Material Science Department, University of Patras, 26504 Rio Patras, Greece ‡Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University in Olomouc, 17 listopadu 1192/12, 771 46 Olomouc, Czech Republic

Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures.

Chemistries that Facilitate Nanotechnology Kim E. Sapsford,† W. Russ Algar, Lorenzo Berti, Kelly Boeneman Gemmill,‡ Brendan J. Casey,† Eunkeu Oh, Michael H. Stewart, and Igor L. Medintz*,‡ †Division of Biology, Department of Chemistry and Materials Science, Office of Science and Engineering Laboratories, U.S. Food and Drug Administration, Silver Spring, Maryland 20993, United States ‡Center for Bio/Molecular Science and Engineering Code 6900 and Division of Optical Sciences Code 5611, U.S. Naval Research Laboratory, Washington, D.C. 20375, United States College of Science, George Mason University, 4400 University Drive, Fairfax, Virginia 22030, United States Department of Biochemistry and Molecular Medicine, University of California, Davis, School of Medicine, Sacramento, California 95817, United States Sotera Defense Solutions, Crofton, Maryland 21114, United States

Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology.

Crystal Engineering and Organometallic Architecture.

The idea1 that fullerenes might be able to encapsulate atoms and molecules has been verified by the successful synthesis of a range of endohedral fullerenes, in which metallic or non-metallic species are trapped inside the carbon cage2,3,4,5,6,7,8,9,10,11,12,13. Metal-containing endohedral fullerenes have attracted particular interest as they might exhibit unusual material properties associated with charge transfer from the metal to the carbon shell. However, current synthesis methods have typical yields of less than 0.5%, and produce multiple endohedral fullerene isomers, which makes it difficult to perform detailed studies of their properties. Here we show that the introduction of small amounts of nitrogen into an electric-arc reactor allows for the efficient production of a new family of stable endohedral fullerenes encapsulating trimetallic nitride clusters, ErxSc3-xN@C80 (x = 0–3). This ‘trimetallic nitride template’ process generates milligram quantities of product containing 3–5% Sc3N@C80, which allows us to isolate the material and determine its crystal structure, and its optical and electronic properties. We find that the Sc3N moiety is encapsulated in a highly symmetric, icosahedral C80 cage, which is stabilized as a result of charge transfer between the nitride cluster and the fullerene cage. We expect that our method will provide access to a range of small-bandgap fullerene materials, whose electronic properties can be tuned by encapsulating nitride clusters containing different metals and metal mixtures.

Small-bandgap endohedral metallofullerenes in high yield and purity

Electron diffraction patterns of the fullerene C 60 in the gaseous state have been obtained by volatilizing it from a newly designed oven-nozzle at 730°C. The many peaks of the experimental radial distribution curve calculated from the scattered intensity are completely consistent with icosahedral symmetry for the free molecule. On the basis of this symmetry assumption, least-squares refinement of a model incorporating all possible interatomic distances led to the values r g (C 1 -C 2 ) = 1.458(6) angstroms (A) for the thermal average bond length within the five-member ring (that is, for the bond fusing five- and six-member rings) and r g (C 1 -C 6 ) = 1.401(10) A for that connecting five-member rings (the bond fusing six-member rings). The weighted average of the two bond lengths and the difference between them are the values 1.439(2) A and 0.057(6) A, respectively. The diameter of the icosahedral sphere is 7.113(10) A. The uncertainties in parentheses are estimated 2σ values.

https://science.sciencemag.org/content/sci/254/5030/410.full.pdf

Bond lengths in free molecules of buckminsterfullerene, c60, from gas-phase electron diffraction.

In the evolving field of fullerenes, nanotubes and endohedral metallofullerenes, the isolated-pentagon rule (IPR)1 is sacrosanct — exceptions have been predicted2,3, but no bare carbon cages with adjacent pentagons have been characterized. Small organic molecules with metal-stabilized fused five-membered rings (pentalenes) have been created4, however, and here we describe a family of non-classical endohedral metallofullerenes with the general structure AxSc3−xN@C68 (where x = 0–2, A is a rare-earth metal, Sc is scandium and N is nitrogen) that has a non-IPR cage of only 68 carbon atoms containing annelated five-membered rings. This internal ring network is metal-stabilized and is accessible for external organic reaction chemistry.

A stable non-classical metallofullerene family

The rotational dynamics of C60 in the solid state have been investigated with carbon-13 nuclear magnetic resonance (13C NMR). The relaxation rate due to chemical shift anisotropy (1/9T1CSA1) was precisely measured from the magnetic field dependence of T1, allowing the molecular reorientational correlation time, τ, to be determined. At 283 kelvin, τ = 9.1 picoseconds; with the assumption of diffusional reorientation this implies a rotational diffusion constant D = 1.8 x 1010 per second. This reorientation time is only three times as long as the calculated τ for free rotation and is shorter than the value measured for C60 in solution (15.5 picoseconds). Below 260 kelvin a second phase with a much longer reorientation time was observed, consistent with recent reports of an orientational phase transition in solid C60. In both phases τ showed Arrhenius behavior, with apparent activation energies of 1.4 and 4.2 kilocalories per mole for the high-temperature (rotator) and low-temperature (ratchet) phases, respectively. The results parallel those found for adamantane.

https://science.sciencemag.org/content/sci/255/5049/1235.full.pdf

Harry C. Dorn

Papers

Small-bandgap endohedral metallofullerenes in high yield and purity

Bond lengths in free molecules of buckminsterfullerene, c60, from gas-phase electron diffraction.

A stable non-classical metallofullerene family

C60 rotation in the solid state: dynamics of a faceted spherical top.

Isolation and Structural Characterization of the Endohedral Fullerene Sc3N@C78