Hierarchical-likelihood approach for nonlinear mixed-effects models

The restricted maximum likelihood (REML) procedure is useful for inferences about variance components in linear mixed models (LMMs). However, its extension to nonlinear mixed models (NLMMs) is often hampered by analytically intractable integrals. For NLMMs various estimation methods have been suggested, but they have suffered from unsatisfactory biases. In this paper we propose a statistically and computationally efficient REML procedure, based upon hierarchical likelihood. Numerical studies show that the proposed method reduces the biases in the existing methods that we studied. We also study how the current REML procedure for LMMs can be modified to compute the proposed estimators.     

Identification of circulating endorepellin LG3 fragment: Potential use as a serological biomarker for breast cancer

Comparative proteome analysis was performed on the cultured media of human nontumor and malignant breast cell lines, Hs578Bst and Hs578T, respectively, in search of a serological biomarker(s) for breast cancer. Proteins in the conditioned media were separated by 2‐D PAGE and then visualized by silver‐staining. Eight proteins changed differentially by more than two‐fold were identified by MALDI‐TOF/TOF MS. Among the proteins identified, the terminal laminin‐like globular (LG3) domain of endorepellin, which was recently reported as an antiangiogenesis factor, was decreased in the cancer cell line. We confirmed the bone morphogenic protein‐1 (BMP‐1) mediated cleavage site on the N‐terminus of endorepellin LG3 fragment. This finding suggests that the LG3 fragment is specifically released by a BMP‐1 driven limited proteolytic process. The protein was also detected in plasma by Western blot analysis and selected reaction monitoring (SRM). The plasma level of the endorepellin LG3 fragment was significantly lower in breast cancer patients compared to healthy donors (p = 0.017; n = 12). The LG3 protein concentration in the control plasma was measured at approximately 3.7 pmol/mL compared to 1.8 pmol/mL in plasma from the cancer patients. We suggest that these results support the potential use of the endorepellin LG3 fragment as a new serological biomarker for breast cancer.     

Synthesis and surface‐active properties of a trisiloxane‐modified oligo(propylene oxide‐block‐ethylene oxide) wetting agent

Polydisperse 1,1,1,3,5,5,5‐heptamethyltrisiloxane‐oligo(propylene oxide‐block‐ethylene oxide) wetting agents were synthesized through the hydrosilylation of 1,1,1,3,5,5,5‐heptamethyltrisiloxane (HMTS) with active hydrogen and allyl oligo(propylene oxide‐block‐ethylene oxide) [allyl oligo(PO‐b‐EO)] with hexachloro dihydrogen platinate(IV) as a catalyst. Allyl oligo(PO‐b‐EO) with a hydrophilic–hydrophobic balance was synthesized through the combination of propylene oxide (PO) and ethylene oxide with allyl alcohol. The wetting agents with a hydrophilic–hydrophobic balance were synthesized. The aqueous solutions of the wetting agents (0.1 wt %) were almost visibly turbid. An increase in the number of hydrophobic groups of HMTS and PO for the wetting agents resulted in a lower critical solution temperature. Lower surface tensions of 20–25 dyn/cm were found above the critical micelle concentration (cmc), and they decreased with an increase in the number of hydrophobic groups. The cmc's were below 0.01 wt %, decreasing with as the number of hydrophobic groups increased. The wetting power and emulsion stability for the oil‐in‐water systems increased as the concentration of the wetting agents increased, and they decreased as the number of hydrophobic groups increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3292–3302, 2004     

Surface modification with waterborne fluorinated anionic polyurethane dispersions

Waterborne fluorinated anionic polyurethane dispersions (FAPUDs) were synthesized from tris(6‐isocyanatohexyl) isocyanurate, N‐ethyl‐N‐2‐hydroxyethyl‐perfluorooctanesulfonamide, poly(oxytetramethylene glycol) (PTMG), dimethylolpropionic acid (DMPA), hexamethylene diisocyanate, 1,4‐butanediol, and two different neutralizing agents (triethylamine and sodium carbonate). Waterborne polyurethane dispersions (PUDs) were synthesized from isophorone diisocyanate, PTMG, DMPA, and ethylenediamine as chain extenders. The particle size of the FAPUDs, based on the fluorine content and degree of neutralization (DN), was measured with dynamic light scattering. So that the surface modification and morphology variations of the PUDs through the addition of the FAPUDs could be observed, the surface energy and thermal properties of the blending films [fluorine PUD mixtures (FPMs)] were measured with contact‐angle analysis and differential scanning calorimetry. The particle size of the FAPUDs increased as the fluorine content in the FAPUDs increased and decreased as the DN increased. The surface energy of the FPM films made from the blending of the FAPUD T series (neutralization with triethylamine) gradually decreased above the critical fluorine concentration (0.02797 wt %). However, for the blending of the FAPUD 25Na series (neutralization with sodium carbonate), the surface energy increased above the critical fluorine concentration (0.02797 wt %) because of the increase in Na salts. The FAPUDs showed the native thermal behavior of the fluorine. However, the thermal properties of the blending films were like those of pure PUDs. This showed that the morphology of the PUDs was rarely unchanged when the FAPUDs were added. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3322–3330, 2002     

Preparation of high‐molecular‐weight poly(N‐vinylcarbazole) by the photoinduced low‐temperature solution polymerization of N‐vinylcarbazole in 1,1,2,2‐tetrachloroethane

For the preparation of high‐molecular‐weight (HMW) poly(N‐vinylcarbazole) (PVCZ) with a narrow molecular weight distribution, N‐vinylcarbazole (VCZ) was solution‐polymerized in 1,1,2,2‐tetrachloroethane (TCE) at ?20, 0, and 20°C with photoinitiation. The effects of the polymerization temperature and the concentrations of the polymerization solvent and photoinitiator on the polymerization behavior and molecular parameters of PVCZ were investigated. A low polymerization temperature with photoirradiation was successful in obtaining HMW PVCZ with a smaller temperature rise during polymerization than that for thermal free‐radical polymerization by azobisisobutyronitrile (AIBN). The photo‐solution‐polymerization rate of VCZ in TCE was proportional to [AIBN]^0.45. The molecular weight was higher and the molecular weight distribution was narrower for PVCZ made at lower temperatures. For PVCZ prepared in TCE at ?20°C with a photoinitiator concentration of 0.00003 mol/mol of VCZ, a weight‐average molecular weight of 920,000 was obtained, with a polydispersity index of 1.46, and the degree of transparency converged to about 99%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2391–2396, 2003     

Magnetic and structural properties of Co ion-implanted GaN

A GaN epilayer was grown on Al/sub 2/O/sub 3/ substrate by metal-organic chemical vapor deposition, and Co/sup -/ ions with a dose of 3/spl times/10/sup 16/ cm/sup -2/ were implanted into GaN at 350/spl deg/C. The implanted samples were postannealed at 700/spl deg/C-900/spl deg/C to recrystallize the samples and to remove implantation damage. We have investigated the magnetic and structural properties of Co ion-implanted GaN by using X-ray diffraction (XRD), superconducting quantum interference device (SQUID) magnetometer, and X-ray photoelectron spectroscopy (XPS). XRD results did not show any peaks associated with the second phase formation, and only the diffraction from the GaN layer and substrate structure were observed. The temperature dependence of magnetization taken in zero-field-cooling and field-cooling conditions showed the features of superparamagnetic system in films annealed at 700/spl deg/C-900/spl deg/C. The magnetization curves at 5 K for samples annealed at 700/spl deg/C-900/spl deg/C exhibits ferromagnetic hysteresis loops, and the highest residual magnetization (M/sub R/) and coercivity (H/sub c/) of M/sub R/=1.5/spl times/10/sup -4/ emu/g and H/sub c/=107 Oe were found in the 800/spl deg/C annealed sample. XPS measurement showed the metallic Co 2p core levels and the metallic valence band spectra for as-implanted and 700/spl deg/C-900/spl deg/C annealed samples. From these, it could be explained that the magnetic property of our films originated from Co and CoGa magnetic clusters.     

Electronic‐Reconstruction‐Enhanced Tunneling Conductance at Terrace Edges of Ultrathin Oxide Films

Quantum mechanical tunneling of electrons across ultrathin insulating oxide barriers has been studied extensively for decades due to its great potential in electronic‐device applications. In the few‐nanometers‐thick epitaxial oxide films, atomic‐scale structural imperfections, such as the ubiquitously existed one‐unit‐cell‐high terrace edges, can dramatically affect the tunneling probability and device performance. However, the underlying physics has not been investigated adequately. Here, taking ultrathin BaTiO₃ films as a model system, an intrinsic tunneling‐conductance enhancement is reported near the terrace edges. Scanning‐probe‐microscopy results demonstrate the existence of highly conductive regions (tens of nanometers wide) near the terrace edges. First‐principles calculations suggest that the terrace‐edge geometry can trigger an electronic reconstruction, which reduces the effective tunneling barrier width locally. Furthermore, such tunneling‐conductance enhancement can be discovered in other transition metal oxides and controlled by surface‐termination engineering. The controllable electronic reconstruction can facilitate the implementation of oxide electronic devices and discovery of exotic low‐dimensional quantum phases.     

Inorganic Polymer Micropillar‐Based Solution Shearing of Large‐Area Organic Semiconductor Thin Films with Pillar‐Size‐Dependent Crystal Size

It is demonstrated that the crystal size of small‐molecule organic semiconductors can be controlled during solution shearing by tuning the shape and dimensions of the micropillars on the blade. Increasing the size and spacing of the rectangular pillars increases the crystal size, resulting in higher thin‐film mobility. This phenomenon is attributed as the microstructure changing the degree and density of the meniscus line curvature, thereby controlling the nucleation process. The use of allylhybridpolycarbosilane (AHPCS), an inorganic polymer, is also demonstrated as the microstructured blade for solution shearing, which has high resistance to organic solvents, can easily be microstructured via molding, and is flexible and durable. Finally, it is shown that solution shearing can be performed on a curved surface using a curved blade. These demonstrations bring solution shearing closer to industrial applications and expand its applicability to various printed flexible electronics.     

Mechanical property of magnesium alloy sheet with hardening deterioration at warm temperatures and its application for failure analysis: Part I - property characterization

The mechanical property of a thin AZ31B Mg alloy sheet (with the thickness of 0.5 mm) was characterized for its anisotropy, temperature-dependent hardening (including its deterioration) and strain rate sensitivity based on simple tension test data measured at 100 °C, 150 °C, 200 °C, 250 °C, respectively, in Part I. As for anisotropy, simple tension tests were performed along three (rolling, transverse and in-between) directions to calibrate the Hill1948 yield function. As for temperature-dependent hardening, the common practice is to characterize hardening only up to the uniform elongation limit and to extrapolate the data to cover the range beyond its limit. In this work, hardening as well as its deterioration (or softening) behavior observed beyond the uniform elongation limit was numerically characterized based on the inverse calibration method, in which strain rate sensitivity was also considered. The mechanical properties were confirmed to properly predict failure by strain localization for all the simple tension tests involved in the characterization procedure. Ultimately, the mechanical properties characterized in Part I were applied in Part II to analyze the failure by strain localization in the cross-shaped cup drawing tests developed as the benchmark problem for the NUMISHEET2011 conference [1].