Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Bis[3‐(trimethyl­silyl)prop­yl] ethyl­enebisphospho­nate,H2DTMSP[EBP]

The title compound (H₂DTMSP[EBP]), C₁₄H₃₆O₆P₂Si₂, was crystallized by the slow evaporation of a solution in a 20:1 mixture of pentane and acetone. The H₂DTMSP[EBP] mole­cule lies about an inversion center. In the solid state, the mol­ecule exists in an anti configuration, with the mol­ecular backbone C—C bond located on an inversion center. The compound exists in the solid state as hydrogen‐bonded infinite sheets in the ab plane, unlike the methyl­ene analogue, which exists as hydrogen‐bonded infinite chains, demonstrating an `even–odd' effect of the length of the backbone alkyl chain.     

Solution-phase, triangular ag nanotriangles fabricated by nanosphere lithography

A novel method to produce solution-phase triangular silver nanoparticles is presented. Ag nanoparticles are prepared by nanosphere lithography and are subsequently released into solution. The resulting nanoparticles are asymmetrically functionalized to produce either single isolated nanoparticles or dimer pairs. The structural and optical properties of Ag nanoparticles have been characterized. Mie theory and the Discrete Dipole Approximation method (DDA) have been used to model and interpret the optical properties of the released Ag nanoparticles.     

Thermal and mechanical properties of PE/organoclay nanocomposites

Polyethylene/montmorillonite clay nanocomposites were obtained via direct melt intercalation. The clay was organically modified with four different types of quaternary ammonium salts. The objective of this work is to study the use of montmorillonite clay in the production of nanocomposites by means on rheological, mechanical and crystallization properties of nanocomposites and to compare to the properties of the matrix and PE/unmodified clay nanocomposites. In general, the tensile test showed that the yield strength and modulus of the nanocomposites are close to the pure PE. Apparently, the mixture with Dodigen salt seems to be more stable than the pure PE and PE/unmodified clay.     

Ultrasensitive single-cell proteomics workflow identifies >1000 protein groups per mammalian cell

We report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.

The combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS) and latest-generation mass spectrometry instrumentation provides dramatically improved single-cell proteome profiling.     

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.     

Molecular chaperones, folding catalysts, and the recovery of active recombinant proteins fromE. coli

The high-level expression of recombinant gene products in the gramnegative bacteriumEscherichia coli often results in the misfolding of the protein of interest and its subsequent degradation by cellular proteases or its deposition into biologically inactive aggregates known as inclusion bodies. It has recently become clear that in vivo protein folding is an energy-dependent process mediated by two classes of folding modulators. Molecular chaperones, such as the DnaK-DnaJ-GrpE and GroEL-GroES systems, suppress off-pathway aggregation reactions and facilitate proper folding through ATP-coordinated cycles of binding and release of folding intermediates. On the other hand, folding catalysts (foldases) accelerate rate-limiting steps along the protein folding pathway such as thecis/trans isomerization of peptidyl-prolyl bonds and the formation and reshuffling of disulfide bridges. Manipulating the cytoplasmic folding environment by increasing the intracellular concentration of all or specific folding modulators, or by inactivating genes encoding these proteins, holds great promise in facilitating the production and purification of heterologous proteins. Purified folding modulators and artificial systems that mimic their mode of action have also proven useful in improving the in vitro refolding yields of chemically denatured polypeptides. This review examines the usefulness and limitations of molecular chaperones and folding catalysts in both in vivo and in vitro folding processes.     

Detection of a biomarker for Alzheimer's disease from synthetic and clinical samples using a nanoscale optical biosensor

A nanoscale optical biosensor based on localized surface plasmon resonance (LSPR) spectroscopy has been developed to monitor the interaction between the antigen, amyloid-beta derived diffusible ligands (ADDLs), and specific anti-ADDL antibodies. Using the sandwich assay format, this nanosensor provides quantitative binding information for both antigen and second antibody detection that permits the determination of ADDL concentration and offers the unique analysis of the aggregation mechanisms of this putative Alzheimer's disease pathogen at physiologically relevant monomer concentrations. Monitoring the LSPR-induced shifts from both ADDLs and a second polyclonal anti-ADDL antibody as a function of ADDL concentration reveals two ADDL epitopes that have binding constants to the specific anti-ADDL antibodies of 7.3 x 10(12) M(-1) and 9.5 x 10(8) M(-1). The analysis of human brain extract and cerebrospinal fluid samples from control and Alzheimer's disease patients reveals that the LSPR nanosensor provides new information relevant to the understanding and possible diagnosis of Alzheimer's disease.