Interfacial assembly inspired by marine mussels and antifouling effects of polypeptoids : a neutron reflection study

Polypeptoid-coated surfaces and many surface-grafted hydrophilic polymer brushes have been proven efficient in antifouling-the prevention of nonspecific biomolecular adsorption and cell attachment. Protein adsorption, in particular, is known to mediate subsequent cell-surface interactions. However, the detailed antifouling mechanism of polypeptoid and other polymer brush coatings at the molecular level is not well understood. Moreover, most adsorption studies focus only on measuring a single adsorbed mass value, and few techniques are capable of characterizing the hydrated in situ layer structure of either the antifouling coating or adsorbed proteins. In this study, interfacial assembly of polypeptoid brushes with different chain lengths has been investigated in situ using neutron reflection (NR). Consistent with past simulation results, NR revealed a common two-step structure for grafted polypeptoids consisting of a dense inner region that included a mussel adhesive-inspired oligopeptide for grafting polypeptoid chains and a highly hydrated upper region with very low polymer density (molecular brush). Protein adsorption was studied with human serum albumin (HSA) and fibrinogen (FIB), two common serum proteins of different sizes but similar isoelectric points (IEPs). In contrast to controls, we observed higher resistance by grafted polypeptoid against adsorption of the larger FIB, especially for longer chain lengths. Changing the pH to close to the IEPs of the proteins, which generally promotes adsorption, also did not significantly affect the antifouling effect against FIB, which was corroborated by atomic force microscopy imaging. Moreover, NR enabled characterization of the in situ hydrated layer structures of the polypeptoids together with proteins adsorbed under selected conditions. While adsorption on bare SiO2 controls resulted in surface-induced protein denaturation, this was not observed on polypeptoids. Our current results therefore highlight the detailed in situ view that NR may provide for characterizing protein adsorption on polymer brushes as well as the excellent antifouling behavior of polypeptoids

Argon annealing of the oxygen-isotope exchanged manganite La_{0.8}Ca_{0.2}MnO_{3+y}

We have resolved a controversial issue concerning the oxygen-isotope shift of the ferromagnetic transition temperature T_{C} in the manganite La_{0.8}Ca_{0.2}MnO_{3+y}. We show that the giant oxygen-isotope shift of T_C observed in the normal oxygen-isotope exchanged samples is indeed intrinsic, while a much smaller shift observed in the argon annealed samples is an artifact. The argon annealing causes the 18O sample to partially exchange back to the 16O isotope due to a small 16O contamination in the Ar gas. Such a contamination is commonly caused by the oxygen outgas that is trapped in the tubes, connectors and valves. The present results thus umambiguously demonstrate that the observed large oxygen isotope effect is an intrinsic property of manganites, and places an important constraint on the basic physics of these materials.Comment: 4 pages, 3 figures, submitted to PR

Ferromagnetic Polarons in La0.5Ca0.5MnO3 and La0.33Ca0.67MnO3

Unrestricted Hartree-Fock calculations on La0.5Ca0.5MnO3 and La0.33Ca0.67MnO3 in the full magnetic unit cell show that the magnetic ground states of these compounds consist of 'ferromagnetic molecules' or polarons ordered in herring-bone patterns. Each polaron consists of either three or five Mn ions separated by O- ions with a magnetic moment opposed to those of the Mn ions. Ferromagnetic coupling within the polarons is strong while coupling between them is relatively weak. Magnetic moments on the Mn ions range between 3.8 and 3.9 Bohr magnetons in La0.5Ca0.5MnO3 and moments on the O- ions are -0.7 Bohr magnetons. Each polaron has a net magnetic moment of 7.0 Bohr magnetons, in good agreement with recently reported magnetisation measurements from electron microscopy. The polaronic nature of the electronic structure reported here is obviously related to the Zener polaron model recently proposed for Pr0.6Ca0.4MnO3 on the basis of neutron scattering data.Comment: 4 pages 5 figure

Cooperation of the Inducible Nitric Oxide Synthase and Cytochrome P450 1A1 in Mediating Lung Inflammation and Mutagenicity Induced by Diesel Exhaust Particles

Diesel exhaust particles (DEPs) have been shown to activate oxidant generation by alveolar macrophages (AMs), alter xenobiotic metabolic pathways, and modify the balance of pro-antiinflammatory cytokines. In this study we investigated the role of nitric oxide (NO) in DEP-mediated and DEP organic extract (DEPE)-mediated inflammatory responses and evaluated the interaction of inducible NO synthase (iNOS) and cytochrome P450 1A1 (CYP1A1). Male Sprague-Dawley rats were intratracheally (IT) instilled with saline, DEPs (35 mg/kg), or DEPEs (equivalent to 35 mg DEP/kg), with or without further treatment with an iNOS inhibitor, aminoguanidine (AG; 100 mg/kg), by intraperitoneal injection 30 min before and 3, 6, and 9 hr after IT exposure. At 1 day postexposure, both DEPs and DEPEs induced iNOS expression and NO production by AMs. AG significantly lowered DEP- and DEPE-induced iNOS activity but not the protein level while attenuating DEPE- but not DEP-mediated pulmonary inflammation, airway damage, and oxidant generation by AMs. DEP or DEPE exposure resulted in elevated secretion of both interleukin (IL)-12 and IL-10 by AMs. AG significantly reduced DEP- and DEPE-activated AMs in IL-12 production. In comparison, AG inhibited IL-10 production by DEPE-exposed AMs but markedly increased its production by DEP-exposed AMs, suggesting that NO differentially regulates the pro- and antiinflammatory cytokine balance in the lung. Both DEPs and DEPEs induced CYP1A1 expression. AG strongly inhibited CYP1A1 activity and lung S9 activity-dependent 2-aminoanthracene mutagenicity. These studies show that NO plays a major role in DEPE-induced lung inflammation and CYP-dependent mutagen activation but a lesser role in particulate-induced inflammatory damage

Pion photoproduction on the nucleon in the quark model

We present a detailed quark-model study of pion photoproduction within the effective Lagrangian approach. Cross sections and single-polarization observables are investigated for the four charge channels, $\gamma p\to \pi^+ n$, $\gamma n\to \pi^- p$, $\gamma p\to \pi^0 p$, and $\gamma n\to \pi^0 n$. Leaving the $\pi N\Delta$ coupling strength to be a free parameter, we obtain a reasonably consistent description of these four channels from threshold to the first resonance region. Within this effective Lagrangian approach, strongly constrainted by the quark model, we consider the issue of double-counting which may occur if additional {\it t}-channel contributions are included.Comment: Revtex, 35 pages, 16 eps figures; version to appear on PR

Spin-Glass State in CuGa2O4\rm CuGa_2O_4

Magnetic susceptibility, magnetization, specific heat and positive muon spin relaxation (\musr) measurements have been used to characterize the magnetic ground-state of the spinel compound $\rm CuGa_2O_4$. We observe a spin-glass transition of the S=1/2 $\rm Cu^{2+}$ spins below $\rm T_f=2.5K$ characterized by a cusp in the susceptibility curve which suppressed when a magnetic field is applied. We show that the magnetization of $\rm CuGa_2O_4$ depends on the magnetic histo Well below $\rm T_f$, the muon signal resembles the dynamical Kubo-Toyabe expression reflecting that the spin freezing process in $\rm CuGa_2O_4$ results Gaussian distribution of the magnetic moments. By means of Monte-Carlo simulati we obtain the relevant exchange integrals between the $\rm Cu^{2+}$ spins in this compound.Comment: 6 pages, 16 figure

Polaron features of the one-dimensional Holstein Molecular Crystal Model

The polaron features of the one-dimensional Holstein Molecular Crystal Model are investigated by improving a variational method introduced recently and based on a linear superposition of Bloch states that describe large and small polaron wave functions. The mean number of phonons, the polaron kinetic energy, the electron-phonon local correlation function, and the ground state spectral weight are calculated and discussed. A crossover regime between large and small polaron for any value of the adiabatic parameter $\omega_0/t$ is found and a polaron phase diagram is proposed.Comment: 12 pages, 2 figure

Colossal magnetooptical conductivity in doped manganites

We show that the current carrier density collapse in doped manganites, which results from bipolaron formation in the paramagnetic phase, leads to a colossal change of the optical conductivity in an external magnetic field at temperatures close to the ferromagnetic transition. As with the colossal magnetoresistance (CMR) itself, the corresponding magnetooptical effect is explained by the dissociation of localized bipolarons into mobile polarons owing to the exchange interaction with the localized Mn spins in the ferromagnetic phase. The effect is positive at low frequencies and negative in the high-frequency region. The present results agree with available experimental observations.Comment: 4 pages, REVTeX 3.0, two eps-figures included in the tex

Integrating fluctuations into distribution of resources in transportation networks

We propose a resource distribution strategy to reduce the average travel time in a transportation network given a fixed generation rate. Suppose that there are essential resources to avoid congestion in the network as well as some extra resources. The strategy distributes the essential resources by the average loads on the vertices and integrates the fluctuations of the instantaneous loads into the distribution of the extra resources. The fluctuations are calculated with the assumption of unlimited resources, where the calculation is incorporated into the calculation of the average loads without adding to the time complexity. Simulation results show that the fluctuation-integrated strategy provides shorter average travel time than a previous distribution strategy while keeping similar robustness. The strategy is especially beneficial when the extra resources are scarce and the network is heterogeneous and lowly loaded.Comment: 14 pages, 4 figure

Isotope Effect for the Penetration Depth in Superconductors

We show that various factors can lead to an isotopic dependence of the penetration depth $\delta$. Non-adiabaticity (Jahn-Teller crossing) leads to the isotope effect of the charge carrier concentration $n$ and, consequently, of $\delta$ in doped superconductors such as the cuprates. A general equation relating the isotope coefficients of $T_c$ and of $\delta$ is presented for London superconductors. We further show that the presence of magnetic impurities or a proximity contact also lead to an isotopic dependence of $\delta$; the isotope coefficient turns out to be temperature dependent, $\beta(T)$, in these cases. The existence of the isotope effect for the penetration depth is predicted for conventional as well as for high-temperature superconductors. Various experiments are proposed and/or discussed.Comment: 11 pages, 8 figures, accepted for publication in Phys. Rev.