AFM nanoindentations of diatom biosilica surfaces

Diatoms have intricately and uniquely nanopatterned silica exoskeletons (frustules) and are a common target of biomimetic investigations. A better understanding of the diatom frustule structure and function at the nanoscale could provide new insights for the biomimetic fabrication of nanostructured ceramic materials and lightweight, yet strong, scaffold architectures. Here, we have mapped the nanoscale mechanical properties of Coscinodiscus sp. diatoms using atomic force microscopy (AFM)-based nanoindentation. Mechanical properties were correlated with the frustule structures obtained from high-resolution AFM and scanning electron microscopy (SEM). Significant differences in the micromechanical properties for the different frustule layers were observed. A comparative study of other related inorganic material including porous silicon films and free-standing membranes as well as porous alumina was also undertaken.     

Fluoride-conversion synthesis of homogeneous actinide oxide solid solutions

The synthesis of (U,Th)O(2) solid solutions at a relatively low temperature of 1100 °C using a new technique is described. First, separate actinide oxides were reacted with ammonium hydrogen fluoride to form ammonium actinide fluorides at room temperature. Subsequently, this fluoride was converted to an actinide oxide solid solution using a two-phase reaction process, which involved heating of the fluoride first at 610 °C in static air followed by heating at 1100 °C in flowing argon. Oxide solid solutions of UO(2) and ThO(2) were synthesized for a ThO(2) content from 10 to 90 wt %. Microscopic investigation showed that the (U,Th)O(2) solid solutions synthesized using this method had high crystallinity and homogeneity up to nanoscale.     

Measuring flux distributions for diffusion in the small-numbers limit

For the classical diffusion of independent particles, Fick's law gives a well-known relationship between the average flux and the average concentration gradient. What has not yet been explored experimentally, however, is the dynamical distribution of diffusion rates in the limit of small particle numbers. Here, we measure the distribution of diffusional fluxes using a microfluidics device filled with a colloidal suspension of a small number of microspheres. Our experiments show that (1) the flux distribution is accurately described by a Gaussian function; (2) Fick's law, that the average flux is proportional to the particle gradient, holds even for particle gradients down to a single particle difference; (3) the variance in the flux is proportional to the sum of the particle numbers; and (4) there are backward flows, where particles flow up a concentration gradient, rather than down it. In addition, in recent years, two key theorems about nonequilibrium systems have been introduced: Evans' fluctuation theorem for the distribution of entropies and Jarzynski's work theorem. Here, we introduce a new fluctuation theorem, for the fluxes, and we find that it is confirmed quantitatively by our experiments.     

Syntheses and characterization of oxygen/sulfur-bridged incomplete cubane-type clusters, [Mo3S4Tp3]+ and [Mo3OS3Tp3]+, and a mixed-metal cubane-type cluster, [Mo3FeS4ClTp3]. X-ray structures of [Mo3S4Tp3]Cl, [Mo3OS3Tp3]PF6, and [Mo3FeS4ClTp3

The reaction of [Mo3S4(H2O)9]4+ (1) with hydrotris(pyrazolyl)borate (Tp) ligands produced [Mo3S4Tp3]Cl x 4 H2O ([3]Cl x 4 H2O) in an excellent yield. An X-ray structure analysis of [3]Cl x 4 H2O revealed that each molybdenum atom bonded to the Tp ligand. We report four salts of 3, [3]Cl x 4 H2O, [3]tof x 2 H2O, [3]PF6 x H2O, and [3]BF4 x 2 H2O in this paper. The solubility and stability of the chloride salt in organic solvents differ completely from those of the other salts. We have also prepared a new compound, [Mo3OS3Tp3]PF6 x H2O ([4]PF6 x H2O), via the reaction of [Mo3OS3(H2O)9]4+ (2) with KTp in the presence of NH4PF6. All the molybdenum atoms bonded to Tp ligand. 1H NMR signals corresponding to nine protons bonded to three pyrazole rings in one Tp were observed in a spectrum (at 253 K) of [3]BF4 x 2 H2O. It shows that cluster 3 has a 3-fold rotation axis in CD2Cl2 solution. Twenty-one 1H NMR signals corresponding to twenty-seven protons bonded to nine pyrazole rings in three Tp ligands were observed in a spectrum (at 233 K) of [4]PF6 x H2O; obviously, 4 has no 3-fold rotation axis, in contrast to 3. The short CH...mu3S distance caused large upfield chemical shifts in the 1H NMR spectra of 3 and 4. The reaction of 3 with metallic iron in CH2Cl2 produced [Mo3FeS4XTp3] (X = Cl (5), Br (6)). X-ray structure analysis of 5 has revealed the existence of a cubane-type core Mo3FeS4. Complex 3 functions as a metal-complex ligand for preparing a novel mixed-metal complex even in nonaqueous solvents. The cyclic voltammogram of 5 shows two reversible one-electron couples (E(1/2) = -1.40 and 0.52 V vs SCE) and two irreversible one-electron oxidation processes (E(pc) = 1.54 and 1.66 V vs SCE).     

A tris(2,2'-bipyridine)ruthenium(II) derivative tethered to a cis-PtCl2(amine)2 moiety: syntheses, spectroscopic properties, and visible-light-induced scission of DNA

A tris(2,2'-bipyridine)ruthenium(II) derivative having two N-(3-ammoniopropyl)carbamoyl pendant units has been prepared and reacted with cis-PtCl2(DMSO)2 (DMSO = dimethyl sulfoxide) to give a heteronuclear Ru(II)Pt(II) dimer having a cis-Pt(II)Cl2(aliphatic amine)2 unit, [Ru(bpy)2(mu-bridge)PtCl2](PF6)2 (bpy = 2,2'-bipyridine, bridge = 4,4'-bis(N-(3-aminopropyl)carbamoyl)-2,2'-bipyridine). The ESI-TOF mass spectrum of the Ru(II)Pt(II) dimer shows a set of signals corresponding to {[Ru(bpy)2(mu-bridge)PtCl2](PF6)}(+) (m/z 1181.1). The MLCT (metal-to-ligand charge transfer) luminescence intensity is enhanced upon the platination of two amine units, presumably due to the formation of a relatively rigid metallocycle. More interestingly, the luminescence intensity is further enhanced by the complexation of the Ru(II)Pt(II) dimer with either 5'-GMP (guanosine 5'-monophosphate disodium salt) or calf thymus DNA. Visible-light-induced scission of supercoiled pBR322 DNA is found to be efficiently enhanced in the presence of the title Ru(II)Pt(II) dimer.     

Construction of a pH-driven supramolecular nanovalve

[Structure: see text] The versatility of supramolecular chemistry has been exploited in constructing nanovalves based on mesoporous silica MCM-41 and the mutual recognition between secondary dialkylammonium ions and dibenzo[24]crown-8 (DB24C8). Naphthalene-containing dialkylammonium threads were tethered to the MCM-41, followed by loading with coumarin 460 and capping with DB24C8. Controlled release of coumarin 460 from the pores of MCM-41 was demonstrated using different bases. The rate of release of coumarin 460 from the nanovalves depends on the size of the base.     

Circular dichroism of optically active poly(dialkylsilane) aggregates in microcapsules

Poly[n-hexyl-(S)-3-methylpentylsilane] aggregates confined in microcapsules to keep the aggregation number and ranging in average polymer mass m(p) in a microcapsule from 2 x 10(-)(16) to 2 x 10(-)(14) g were studied by circular dichroism measurements in ethanol (a nonsolvent) and tetrahydrofuran (an associative solvent at low temperature) at various temperatures. The weight-average molecular weight M(w) and the polydispersity index (the ratio of M(w) to the number-average molecular weight) of the polysilane sample were 6.6 x 10(4) and 1.07, respectively, and the average number of polymer molecules in each capsule was estimated to be 1.9 x 10(3) for m(p) = 2 x 10(-)(16) g and 1.7 x 10(5) for m(p) = 2 x 10(-)(14) g. The size of each aggregate did not affect the optical activity because the circular dichroism thus obtained was proportional to m(p) under the same conditions in the investigated m(p) range; on the other hand, the peak height of the circular dichroism in tetrahydrofuran had a significant hysteresis between 0 and 25 degrees C. Moreover, the circular dichroism appreciably reflected the prepared method, that is, the temperature and solvent; in other words, the aggregates memorized the initial conditions in their stacking structures.     

Stern-Gerlach experiments of one-dimensional metal-benzene sandwich clusters: Mn(C6H6)m (M = Al, Sc, Ti, and V)

A molecular beam of multilayer metal-benzene organometallic clusters Mn(C6H6)m (M = Al, Sc, Ti, and V) was produced by a laser vaporization synthesis method, and their magnetic deflections were measured. Multidecker sandwich clusters of transition-metal atoms and benzene Scn(C6H6)n+1 (n = 1, 2) and Vn(C6H6)n+1 (n = 1-4) possess magnetic moments that increase monotonously with n. The magnetic moments of Al(C6H6), Scn(C6H6)n+1, and Vn(C6H6)n+1 are smaller than that of their spin-only values as a result of intracluster spin relaxation, an effect that depends on the orbital angular momenta and bonding characters of the orbitals containing electron spin. While Ti(C6H6)2 was found to be nonmagnetic, Tin(C6H6)n+1 (n = 2, 3) possess nonzero magnetic moments. The mechanism of ferromagnetic spin ordering in M2(C6H6)3 (M = Sc, Ti, V) is discussed qualitatively in terms of molecular orbital analysis. These sandwich species represent a new class of one-dimensional molecular magnets in which the transition-metal atoms are formally zerovalent.     

Shape memory and pseudoelasticity in metal nanowires

Structural reorientations in metallic fcc nanowires are controlled by a combination of size, thermal energy, and the type of defects formed during inelastic deformation. By utilizing atomistic simulations, we show that certain fcc nanowires can exhibit both shape memory and pseudoelastic behavior. We also show that the formation of defect-free twins, a process related to the material stacking fault energy, nanometer size scale, and surface stresses is the mechanism that controls the ability of fcc nanowires of different materials to show a reversible transition between two crystal orientations during loading and thus shape memory and pseudoelasticity.