New class of biodegradable polymers formed from reactions of an inorganic functional group

Although numerous small molecules have been synthesized with sulfenamide bonds (R(2)N-SR), this is the first report of the synthesis of polysulfenamides. These polymers are readily synthesized at room temperature using secondary diamines and dithiosuccinimides. The dithiosuccinimides were readily synthesized in one step by the reaction of dithiols such as HS(CH(2))(6)SH with N-chlorosuccinimide. The resulting dithiosuccinimides were either recrystallized or readily purified by chromatography on silica gel and required no special handling. The conversions of polymerization ranged from 95 to 98%, and the molecular weights of the polymer reached as high as 6,300 g mol(-1). The sulfenamide bond was very stable in organic solvents, and no degradation was observed under atmospheric conditions in C(6)D(6) for 30 days. In contrast, the sulfenamide bond readily decomposed in less than 12 h in D(2)O. Polysulfenamides were fabricated into micron-sized particles loaded with dye and endocytosed into JAWSII immature dendritic and HEK293 cells. Polysulfenamides represent a new class of polymers that are readily synthesized, stable in aprotic solvents, and readily degrade in water.     

Engineered bacterially expressed polypeptides: assembly into polymer particles with tailored degradation profiles

In nature, the sequence of amino acids in a protein is determined by the genetic code. Biosynthesis of polypeptides by bacteria can be used to exploit this natural process to afford exact control over properties such as molecular weight, chemical functionality, and structure. It is demonstrated how control over the positioning of functional groups can be used to tune the degradation of assembled polypeptide particles (see scheme).     

Muon Knight shift and zero-field relaxation in (U,Th)Be13

We report μ⁺ zero-field relaxation and Knight shift studies of the heavy-fermion superconductors U_1−xTh_xBe₁₃, x=0 and 0.033. The Knight shift in UBe₁₃ shows a strong decrease as the temperature is reduced in the superconducting state, unlike U_0.967Th_0.033Be₁₃ in which the shift remains at about the normal state value. If the superconducting state in UBe₁₃ has odd-parity, the decrease of K_μ below T_c suggests that the order parameter is pinned to the lattice. Either spin-orbit scattering or the existence of two distinct superconducting states with different spin susceptibilities in the (U,Th)Be₁₃ system would explain the differences observed in the Th-doped and pure UBe₁₃ materials. The latter hypothesis would exclude conventional BCS superconductivity. No evidence for magnetic order is seen in the zero-field relaxation rate for either material down to 0.3 K.     

Protecting workers and the environment: An environmental NGO’s perspective on nanotechnology

Nanotechnology, the design and manipulation of materials at the atomic scale, may well revolutionize many of the ways our society manufactures products, produces energy, and treats diseases. New materials based on nanotechnology are already reaching the market in a wide variety of consumer products. Some of the observed properties of nanomaterials call into question the adequacy of current methods for determining hazard and exposure and for controlling resulting risks. Given the limitations of existing regulatory tools and policies, we believe two distinct kinds of initiatives are needed: first, a major increase in the federal investment in nanomaterial risk research; second, rapid development and implementation of voluntary standards of care pending development of adequate regulatory safeguards in the longer term. Several voluntary programs are currently at various stages of evolution, though the eventual outputs of each of these are still far from clear. Ultimately, effective regulatory safeguards are necessary to provide a level playing field for industry while adequately protecting human health and the environment. This paper reviews the existing toxicological literature on nanomaterials, outlines and analyzes the current regulatory framework, and provides our recommendations, as an environmental non-profit organization, for safe nanotechnology development.     

Nearly isotropic photonic bandgap structures in two dimensions

It is suggested that a material with a novel spatial dielectric distribution can exhibit a bandgap that is approximately independent of propagation angle. This independence is accomplished by development of the dielectric constant from reflection vectors of equal strength that are ideally equispaced in angle.     

Muon bonding sites in rare earth orthoferrites

A muon site search has been performed for the RFeO₃ series based on a calculation of dipole fields and assumptions that a μ-0 bond is formed at identical sites in each sample. The site previously identified by Holzschuh et al. /1/ has been verified and additional sites located which together explain all the observed μSR frequencies in the orthoferrites. Effects due to muon motion and covalent contributions to the internal fields are briefly discussed.     

Using oxidative crosslinking and proximity labeling to quantitatively characterize protein-protein and protein-Peptide complexes

The quantitative analysis of protein-protein and protein-peptide complexes is of fundamental importance in biochemistry. We report here that nickel-catalyzed proximity biotinylation and Ru(II)(bpy)(3)(2+)-mediated oxidative crosslinking can be used to measure the equilibrium dissociation constant and stoichiometry of protein complexes. Only small amounts of protein are required, neither of the binding partners must be immobilized on a surface, and no special instrumentation is necessary. This chemistry should provide a useful complement to existing methods for the analysis of protein-protein and protein-peptide interactions.     

Label Free Fluorometric Characterization of DNA Interaction with Cholate Capped Gold Nanoparticles Using Ethidium Bromide as a Fluorescent Probe

We demonstrated label free ethidium bromide assisted characterization of DNA interaction with cholate capped AuNPs. Interactions between ss/ds DNA and AuNPs with two different lengths (0.5 and 0.85 kb) were analyzed through fluorescence spectrophotometer and agrose gel electrophoresis analysis. Further results were confirmed by UV–globally visible spectrophotometer, DLS and TEM. As 0.5 and 0.85 kb of ssDNA effectively interacted with AuNPs through the van der Waals interaction which consequently led to the prevention of salt induced aggregation, EtBr intercalations as well as fluorescence shift with less binding constant 0.098 and 0.108 μM, respectively. On the contrary, the same length of dsDNA (0.5 and 0.85 kb) not interacted with AuNPs which led to the NPs aggregation, EtBr intercalation as well as fluorescence shift with increased binding constant 0.166 and 0.599 μM, respectively. This approach helped to understand the mode of interactions of DNA with cholate capped AuNPs without any modifications in a simple method and the results could be readout through the naked eye under the UV transilluminator. Figure

Fluorometric characterization of interaction of different lengths of ss/dsDNA with cholate capped AuNPs using EtBr as fluorescence probe     

Muon spin relaxation and knight shift in the heavy-fermion superconductor UPt3

Positive muon spin relaxation experiments have been conducted on the heavy-fermion superconductor UPt₃ in both the normal and superconducting states for zero, transverse, and longitudinally applied magnetic fields. Below 6 K in zero applied field, the μ⁺ relaxation rate is approximately twice that expected from¹⁹⁵Pt nuclear dipolar relaxation alone. Transverse- and longitudinal-field measurements show that the observe relaxation rate depends on magnetic field and is quasistatic in origin. It is suggested that the onset of very weak (≈10⁻³ μ_B/U atom) magnetic ordering below approximately 6 K is responsible for the observed increase in the relaxation rate. μ⁺ Knight shift measurements in the normal state of UPt₃ show a temperature dependent shift K_μ which tracks the bulk susceptibility X. From the K_μ vs. X plot, a μ⁺ hyperfine field of approximately 100 Oe/μ_B is extracted.