Structural information on nanometer-sized gold particles has been limited, due in part to the problem of preparing homogeneous material. Here we report the crystallization and x-ray structure ...determination of a p-mercaptobenzoic acid (p-MBA)-protected gold nanoparticle, which comprises 102 gold atoms and 44 p-MBAs. The central gold atoms are packed in a Marks decahedron, surrounded by additional layers of gold atoms in unanticipated geometries. The p-MBAs interact not only with the gold but also with one another, forming a rigid surface layer. The particles are chiral, with the two enantiomers alternating in the crystal lattice. The discrete nature of the particle may be explained by the closing of a 58-electron shell.
Full text
Available for:
BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
Synthesis, characterization, and functionalization of self-assembled, ligand-stabilized gold nanoparticles are long-standing issues in the chemistry of nanomaterials. Factors driving the ...thermodynamic stability of well documented discrete sizes are largely unknown. Herein, we provide a unified view of principles that underlie the stability of particles protected by thiolate (SR) or phosphine and halide (PR₃, X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au₁₀₂(SR)₄₄, Au₃₉(PR₃)₁₄X₆⁻, Au₁₁(PR₃)₇X₃, and Au₁₃(PR₃)₁₀X₂³⁺, where X is either a halogen or a thiolate. Attributable to a compact, symmetric core and complete steric protection, each compound has a filled spherical electronic shell and a major energy gap to unoccupied states. Consequently, the exceptional stability is best described by a "noble-gas superatom" analogy. The explanatory power of this concept is shown by its application to many monomeric and oligomeric compounds of precisely known composition and structure, and its predictive power is indicated through suggestions offered for a series of anomalously stable cluster compositions which are still awaiting a precise structure determination.
Full text
Available for:
BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
The synthesis of Au102(p-MBA)44 nanoparticles on a preparative scale in high yield is described. Various analytical methods are shown to give results consistent with the composition and known ...structure of the particles, showing the preparation is essentially homogeneous, and attesting to the validity of the methods as well. Derivatization of the particles with proteins and DNA is demonstrated, and conditions are described for imaging individual particles by cryo-EM at low electron dose, close to focus, conditions optimal for recording high-resolution details.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
Water-soluble monolayer-protected gold clusters (MPCs) have been an object of investigation by many research groups since their first syntheses were reported in 1998 and 1999. The basic requirements ...for a ligand to form a monolayer protecting a gold cluster were established some time ago for alkanethiolate MPCs, but there has been no such information published for water-soluble MPCs. We identify 6 new ligands capable of forming water-soluble MPCs, as well as 22 water-soluble ligands that fail to form MPCs. Our findings contribute not only to the definition of the requirements for MPC formation but also to the variety of MPCs available for applications in chemistry and biology.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
A general method of rigid, specific labeling of proteins with gold clusters has been devised. The method relies on the conjugation of a glutathione monolayer-protected gold cluster (MPC) with a ...single chain Fv antibody fragment (scFv), mutated to present an exposed cysteine residue. Efficient formation of a gold−thiolate bond between the MPC and scFv depends on activation of the gold cluster by chemical oxidation. Once formed, the MPC−scFv conjugate is treated with a reductant to quench cluster reactivity. The procedure has been performed with an MPC with an average Au71 core and an scFv directed against a tetrameric protein, the influenza neuraminidase. A complex of the MPC−scFv conjugate with the neuraminidase was isolated, and the presence of four gold clusters was verified by cryoelectron microscopy.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
By adjustment of solvent conditions for synthesis, virtually monodisperse 4-mercaptobenzoic acid (p-MBA) monolayer-protected gold nanoparticles, 2 and 3 nm in diameter, were obtained. Large single ...crystals of the 2 nm particles could be grown from the reaction mixture. Uniformity was also demonstrated by the formation of two-dimensional arrays and by quantitative high-angle annular dark-field scanning transmission electron microscopy. The 2 and 3 nm particles were spontaneously reactive for conjugation with proteins and DNA, and further reaction could be prevented by repassivation with glutathione. Conjugates with antibody Fc fragment could be used to identify TAP-tagged proteins of interest in electron micrographs, through the binding of a pair of particles to the pair of protein A domains in the TAP tag.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
One of the largest mysteries of the brain lies in understanding how higher-level computations are implemented by lower-level operations in neurons and synapses. In particular, in many brain regions ...inhibitory interneurons represent a diverse class of cells, the individual functional roles of which are unknown. We discuss here how the operations of inhibitory interneurons influence the behavior of a circuit, focusing on recent results in the vertebrate retina. A key role in this understanding is played by a common representation of the visual stimulus that can be applied at different stages. By considering how this stimulus representation changes at each location in the circuit, we can understand how neuron-level operations such as thresholds and inhibition yield circuit-level computations such as how stimulus selectivity and gain are controlled by local and peripheral visual stimuli.
Sensory stimuli have varying statistics influenced by both the environment and by active sensing behaviors that rapidly and globally change the sensory input. Consequently, sensory systems often ...adjust their neural code to the expected statistics of their sensory input to transmit novel sensory information. Here, we show that sudden peripheral motion amplifies and accelerates information transmission in salamander ganglion cells in a 50 ms time window. Underlying this gating of information is a transient increase in adaptation to contrast, enhancing sensitivity to a broader range of stimuli. Using a model and natural images, we show that this effect coincides with an expected increase in information in bipolar cells after a global image shift. Our findings reveal the dynamic allocation of energy resources to increase neural activity at times of expected high information content, a principle of adaptation that balances the competing requirements of conserving spikes and transmitting information.
PDF
