Thin‐Film Infrared Spectroscopy of Acetonitrile

Acetonitrile and [D₃]acetonitrile in the vicinal region of a planar AgX fiber contain linear dipole–dipole linked oligomers as shown by 1) comparison of infrared band intensity ratios in the gaseous and condensed phases and 2) remarkable plots of absorbance (C? N stretch) versus time during evaporation from an AgX planar fiber element. The plots (CH₃CN 2252 cm^?1, CD₃CN 2262 cm^?1) reveal the presence of octamers, hexamers, tetramers, and dimers along with some heptamer, trimer, and monomer structures. A novel isotope effect arises from the somewhat smaller size of the CD₃CN resulting in an increase in the CN band intensity. The organized oligomers may be termed pseudocrystals and are the main components responsible for absorption intensity in the infrared spectrum of acetonitrile, on the AgX planar fiber or in an IR cell.     

Laccase Biosensor on Monolayer‐Modified Gold Electrode

Laccase enzymes from two different sources, namely, tree laccase from Rhus vernicifera and fungal laccase from Coriolus hirsutus were used for the development of biosensor for catechol. Laccase was immobilized onto the amine terminated thiol monolayers on gold surface by glutaraldehyde coupling. From the different thiol monolayers investigated, cystamine was found to be optimal with respect to sensitivity, stability, reproducibility, and other electrochemical properties of the enzyme electrode. Linear calibration in the range between 1 and 400 μM for catechol was obtained for fungal laccase covalently coupled on the electrode surface. The kinetic parameters determined using the Lineweaver‐Burk and Eadie‐Hofstee plots were K_m=0.65 mM and V_max=24.5 μA for fungal laccase compared to K_m=5.4 mM and V_max=6.6 μA for tree laccase on cystamine monolayer. The electrode showed good stability for 1 month without loosing appreciable activity when stored dry in a refrigerator at ?20 °C.     

Synthesis,Liquid‐Crystalline Properties,and Supramolecular Nanostructures of Dendronized Poly(isocyanide)s and Their Precursors

A series of novel dendronized π‐conjugated poly(isocyanide)s were synthesized successfully by using a Pd? Pt μ‐ethynediyl dinuclear complex ([ClPt{P(C₂H₅)₃}₂C?CPt{P(C₂H₅)₃}₂Cl]) as the initiator. The polymerizations of the dendronized monomers follow first‐order kinetics, indicating that living polymerization takes place. The obtained polymers exhibit narrow polydispersities in the range of 1.03–1.20. Thermal properties of the poly(isocyanide)s as well as their isocyanide monomers and precursors with formamido (HCONH‐) moieties as apexes were investigated by using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide‐angle X‐ray diffraction (WAXD). Both the peripheries and the apex groups of the dendrons affect the formation of supramolecular column and/or cubic phases of the precursors and monomers. The formamido precursor forms a liquid‐crystalline phase due to intermolecular hydrogen bonding. The isocyanide monomer lacks this hydrogen‐bonding ability and does not display an organized mesophase. All of the rigid poly(isocyanide)s with the monodendrons exhibit columnar liquid‐crystalline phases. Interestingly, cylindrical structures of a poly(isocyanide) were directly visualized by using transmission electron microscopy (TEM).     

Predicting the shape and structure of face-centered cubic gold nanocrystals smaller than 3 nm.

Although a number of computational studies have examined the relative stability of icosahedral and decahedral gold clusters from 1 to 3 nm in size, few studies have focussed on the variety of face-centered cubic (fcc) nanoparticles in this size regime. In most cases small fcc gold particles are assumed to adopt the truncated octahedral shape, but in light of the fact that the shape and structure of gold nanoparticles is known to vary, the relative stability of fcc polyhedra may change with size. Presented here are results of first-principles calculations investigating the preferred shape of gold particles less than 3 nm in size. Our results indicate that the equilibrium shape of fcc gold nanoparticles less than 1 nm is the cuboctahedron, but this shape rapidly becomes energetically unstable with respect to the truncated octahedron, octahedron and truncated cube shapes as the size increases.     

DNA codes for nanoscience

The nanometer scale is a special place where all sciences meet and develop a particularly strong interdisciplinarity. While biology is a source of inspiration for nanoscientists, chemistry has a central role in turning inspirations and methods from biological systems to nanotechnological use. DNA is the biological molecule by which nanoscience and nanotechnology is mostly fascinated. Nature uses DNA not only as a repository of the genetic information, but also as a controller of the expression of the genes it contains. Thus, there are codes embedded in the DNA sequence that serve to control recognition processes on the atomic scale, such as the base pairing, and others that control processes taking place on the nanoscale. From the chemical point of view, DNA is the supramolecular building block with the highest informational content. Nanoscience has therefore the opportunity of using DNA molecules to increase the level of complexity and efficiency in self-assembling and self-directing processes.     

Improving MCM‐41 as a Nitrosamines Trap through a One‐Pot Synthesis

Copper oxide was incorporated into MCM‐41 by a one‐pot synthesis under acidic conditions to prepare a new mesoporous nitrosamines trap for protection of the environment. The resulting composites were characterized by XRD, N₂ adsorption–desorption, and H₂ temperature‐programmed reduction techniques, and their adsorption capabilities were assessed in the gaseous adsorption of N‐nitrosopyrrolidine (NPYR). The adsorption isotherms were consistent with the Freundlich equation. The copper salt was deposited onto MCM‐41 during the evaporation stage and was fixed on the host in the calcination process that followed. MCM‐41 was able to capture NPYR in air below 373 K but not at 453 K. Loading of copper oxide on MCM‐41 greatly improved its adsorption capability at elevated temperatures. The influence of the incorporation of copper into MCM‐41 samples and the adsorption behavior of these samples are discussed in detail.     

Nanotechnology with soft materials.

Nature exploits self-organization of soft materials in many ways, to produce cell membranes, biopolymer fibers and viruses, to name just three. Mankind is now able to design materials at the nanoscale, whether through atom-by-atom or molecule-by-molecule methods (top-down) or through self-organization (bottom-up). The latter method encompasses soft nanotechnology. Self-organization of soft materials can be exploited to create a panoply of nanostructures for diverse applications. The richness of structures results from the weak ordering because of noncovalent interactions. Thus, thermal energy is important as it enables transitions between phases with differing degrees of order. The power of self-organization may be harnessed most usefully in a number of nanotechnology applications, which include the preparation of nanoparticles, the templating of nanostructures, nanomotor design, the exploitation of biomineralization, and the development of functionalized delivery vectors.     

Templateless assembly of molecularly aligned conductive polymer nanowires: a new approach for oriented nanostructures

Although oriented carbon nanotubes, oriented nanowires of metals, semiconductors and oxides have attracted wide attention, there have been few reports on oriented polymer nanostructures such as nanowires. In this paper we report the assembly of large arrays of oriented nanowires containing molecularly aligned conducting polymers (polyaniline) without using a porous membrane template to support the polymer. The uniform oriented nanowires were prepared through controlled nucleation and growth during a stepwise electrochemical deposition process in which a large number of nuclei were first deposited on the substrate using a large current density. After the initial nucleation, the current density was reduced stepwise in order to grow the oriented nanowires from the nucleation sites created in the first step. The usefulness of these new polymer structures is demonstrated with a chemical sensor device for H(2)O(2), the detection of which is widely investigated for biosensors. Finally, we demonstrated that controlled nucleation and growth is a general approach and has potential for growing oriented nanostructures of other materials.     

Strong coupling expansion for classical statistical dynamics

We discuss the simple, randomly driven systemdx/dt = –x –x³ +f(t), wheref(t) is a Gaussian random function or stirring force with f(t)f(t) = (t – t). We show how to obtain approximately the coefficients of the expansion of the equal-time Green's functions as power series in (1/R)ⁿ, whereR is the internal Reynolds number ()^1/2/, by using a new expansion for the path integral representation of the generating functional for the correlation functions. Exploiting the fact that the action for the randomly driven system is related to that of a quantum mechanical anharmonic oscillator with Hamiltonianp ²/2 +m ² x ²/2 +vx ⁴ +x ⁶/2, we evaluate the path integral on a lattice by assuming that thex ⁶ term dominates the action. This gives an expansion of the lattice theory Green's functions as power series in 1/(a)^1/3, wherea is the lattice spacing. Using Padé approximants to extrapolate toa = 0, we obtain the desired large-Reynolds-number expansion of the two-point function.Supported financially by the National Science Foundation and the U.S. Department of Energy.