Rhodium dimers with 2,2-dimethyl-1,3-diisocyano and bis(diphenylphosphino)methane bridging ligands

Four rhodium dimers have been synthesized with a bridging diisocyanide ligand, dmb (2,2-dimethyl-1,3-diisocyanopropane): [Rh2(dmb)4](BPh4)2, [Rh2(dmb)4Cl2]Cl2, [Rh2(dmb)4I2](PF6)2, and [Rh2(dmb)2(dppm)2](BPh4)2 (dppm = bis(diphenylphosphino)methane). The complexes have been characterized by elemental analysis and mass spectrometry, as well as UV-visible, IR, and 1H NMR spectroscopies. X-ray crystal structures of the rhodium(I) complexes, [Rh2(dmb)4](BPh4)2 . 1.5CH3CN (3.2330(4), 3.2265(4) A) and [Rh2(dmb)2(dppm)2](BPh4)2.0.5CH3OH . 0.2H2O (3.0371(5) A), confirm the existence of short Rh...Rh interactions. The metal-metal separation for the rhodium(II) adduct, [Rh(2)(dmb)4Cl2]Cl2.6CHCl3 (2.8465(6) A), is consistent with a formal Rh-Rh bond. For the two luminescent rhodium(I) dimers and six previously investigated diisocyano-bridged dimers with and without dppm ligands, the intense spin-allowed dsigma-->psigma absorption band maximum shifts to longer wavelengths with decreasing Rh...Rh separation, and there is an approximate correlation between band energy and the inverse of the metal-metal separation cubed. Both [Rh2(dmb)4]2+ and [Rh2(dmb)4(dppm)2]2+ undergo oxidative addition in the presence of iodine. In the conversion of [Rh2(dmb)4]2+ to [Rh2(dmb)4I2]2+, the observed intermediate is tentatively assigned to a tetramer composed of two rhodium dimers. In the case of [Rh2(dmb)2(dppm)2]2+, no intermediate was detected.     

Studies on the effect of solvents on self-assembled monolayers formed from organophosphonic acids on indium tin oxide

The preparation of self-assembled monolayers (SAMs) of organophosphonic acids on indium tin oxide (ITO) surfaces from different solvents (triethylamine, ethyl ether, tetrahydofuran (THF), pyridine, acetone, methanol, acetonitrile, dimethyl sulfoxide (DMSO), or water) has been performed with some significant differences observed. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and contact angle measurement demonstrated that the quality of SAMs depends critically on the choice of solvents. Higher density, more stable monolayers were formed from solvents with low dielectric constants and weak interactions with the ITO. It was concluded low dielectric solvents that were inert to the ITO gave monolayers that were more stable with a higher density of surface bound molecules because higher dielectric constant solvents and solvents that coordinate with the surface disrupted SAM formation.     

Impeding hohlraum plasma stagnation in inertial-confinement fusion

This Letter reports the first time-gated proton radiography of the spatial structure and temporal evolution of how the fill gas compresses the wall blowoff, inhibits plasma jet formation, and impedes plasma stagnation in the hohlraum interior. The potential roles of spontaneously generated electric and magnetic fields in the hohlraum dynamics and capsule implosion are discussed. It is shown that interpenetration of the two materials could result from the classical Rayleigh-Taylor instability occurring as the lighter, decelerating ionized fill gas pushes against the heavier, expanding gold wall blowoff. This experiment showed new observations of the effects of the fill gas on x-ray driven implosions, and an improved understanding of these results could impact the ongoing ignition experiments at the National Ignition Facility.     

Critical point coupling and proximity effects in ^{4}he at the superfluid transition

We report measurements of the superfluid fraction ρ_{s}/ρ and specific heat c_{p} near the superfluid transition of ^{4}He when confined in an array of (2 μm)^{3} boxes at a separation of S=2 μm and coupled through a 32.5?nm film. We find that c_{p} is strongly enhanced when compared with data where coupling is not present. An analysis of this excess signal shows that it is proportional to the finite-size correlation length in the boxes ξ(t,L), and it is measurable as far as S/ξ～30-50. We obtain ξ(0,L) and the scaling function (within a constant) for ξ(t,L) in an L^{3} box geometry. Furthermore, we find that ρ_{s}/ρ of the film persists a full decade closer to the bulk transition temperature T_{λ} than a film uninfluenced by proximity effects. This excess in ρ_{s}/ρ is measurable even when S/ξ>100, which cannot be understood on the basis of mean field theory.     

Arginine topology controls escape of minimally cationic proteins from early endosomes to the cytoplasm

Proteins represent an expanding class of therapeutics, but their actions are limited primarily to extracellular targets because most peptidic molecules fail to enter cells. Here we identified two small proteins, miniature protein 5.3 and zinc finger module ZF5.3, that enter cells to reach the cytosol through rapid internalization and escape from Rab5+ endosomes. The trafficking pathway mapped for these molecules differs from that of Tat and Arg(8), which require transport beyond Rab5+ endosomes to gain cytosolic access. Our results suggest that the ability of 5.3 and ZF5.3 to escape from early endosomes is a unique feature and imply the existence of distinct signals, encodable within short sequences, that favor early versus late endosomal release. Identifying these signals and understanding their mechanistic basis will illustrate how cells control the movement of endocytic cargo and may allow researchers to engineer molecules to follow a desired delivery pathway for rapid cytosolic access.     

Ultrasensitive electrochemical detection of prostate-specific antigen (PSA) using gold-coated magnetic nanoparticles as 'dispersible electrodes'

Herein, we demonstrate the use of modified gold-coated magnetic nanoparticles as 'dispersible electrodes' which act as selective capture vehicles for electrochemical detection of prostate-specific antigen (PSA). A key advantage of this system is the ability to quantify non-electrochemical active analytes such as proteins with unprecedented detection limits and fast response times.     

An Improved Upper Bound on the Total Restrained Domination Number in Cubic Graphs

In this paper, we continue the study of total restrained domination in graphs. A set S of vertices in a graph G = (V, E) is a total restrained dominating set of G if every vertex of G is adjacent to some vertex in S and every vertex of ${V {\setminus} S}$ is adjacent to a vertex in ${V {\setminus} S}$ . The minimum cardinality of a total restrained dominating set of G is the total restrained domination number γ _tr(G) of G. Jiang et?al. (Graphs Combin 25:341–350, 2009) showed that if G is a connected cubic graph of order n, then γ _tr(G) ≤ 13n/19. In this paper we improve this upper bound to γ _tr(G) ≤ (n?+?4)/2. We provide two infinite families of connected cubic graphs G with γ _tr(G) = n/2, showing that our new improved bound is essentially best possible.