Thermal stability study of conductive polyaniline/polyimide blend films on their conductivity and ESR measurement

Conductivity stability at thermal environment of conductive polyaniline‐complexes/polyimide (PANI‐complexes/PI) blends, which were doped by camphorsulfonic acid (CSA) and dodecylbenzenesulfonic acid (DBSA), respectively, were investigated by conductivity measurements, electron spin resonance (ESR) spectra, differential and scanning thermometer (DSC). In the conversion process of PANI/Polyamic acid (PAA) to PANI/PI, the blend endeavored some kinds of alteration such as decomplexation of moisture and solvent, dissociation of dopant, crosslinking of PANI chain, and the imidization of PAA chain. PANI‐DBSA/PI showed higher thermal stability of conductivity than PANI‐CSA/PI, and both samples showed nearly linear decay of conductivity with increasing temperature showing greatly enhancement of conductivity stability. When they were exposed at near or over glass transition temperature, the conductivity decay became faster. The conductivity stability at base environment was also higher for PANI‐DBSA/PI due to difficulty in accessing of hydroxyl ion to PANI, which were resulted from dopant. DBSA‐doped blends showed increased polaron mobility and concentration at relatively high temperature, which led to extremely higher conductivity and its stability at high temperature. Copyright © 2002 John Wiley & Sons, Ltd.     

Effect of the linear siloxane chain in cyclic silsesquioxane (CSSQ) on the mechanical/electrical property of the thin films

Several kinds of cyclic silsesquioxane (CSSQ) precursors containing linear siloxane chain were prepared to improve both the mechanical properties of their thin films and the compatibility with heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin (tCD) as a porogen. The precursors were synthesized using a hydrolysis/condensation reaction with 2,4,6,8-tetramethyl-2,4,6,8-tetra (trimethoxysilylethyl) cyclotetrasiloxane (cyclic monomer) and three kinds of linear siloxane monomers. As the linear siloxane chain length increases in the CSSQ precursors, the compatibility between the CSSQ precursor and tCD molecules improved due to the chain flexibility of the precursor. Moreover, the mechanical strength of the CSSQ precursor (4ST37) containing linear tetrasiloxane was the best among the prepared precursors. The enhancement of mechanical property might also be attributed to the content of Si-OH groups as well as the chain flexibility, which could help the crosslinking reaction of Si-OH groups in the film curing process.     

TMR of double spin-valve type AF/FM/I/FM/I/FM/AF magnetic tunneling junctions

An unusually large enhancement of TMR at 77 K was observed in double barrier tunnel junctions (DBTJ). This is explained with extended Julliere's model which yields a twice larger TMR value. When the spin coherence length is much smaller at higher temperature, DBTJ is shown to work as a series of two single barrier tunnel junctions.     

Conformational preferences and pKa value of cysteine residue

The conformational preferences of the Cys dipeptides with thiol and thiolate groups (Ac-Cys-NHMe and Ac-Cys (-)-NHMe, respectively) and the apparent (i.e., macroscopic) p K a value of the Cys dipeptide have been studied at the hybrid density functional B3LYP/6-311++G(d,p)//B3LYP/6-31+G(d) level with the conductor-like polarizable continuum model in the gas phase and in water. The hydrogen bonds and/or favorable interactions between the backbone and the thiol group of the side chain resulted in the different conformational preferences of the Cys and Cys (-) dipeptides from those of the Ala dipeptide in the gas phase and in water, although the preferred conformations of the Cys dipeptide are in part similar to those of the Ala dipeptide. In particular, the interactions between the thiolate group and the backbone amide groups appear to play a role in stabilizing the alpha- or 3 10-helical conformations for the Cys (-) dipeptide in the gas phase and in water. The p K a value of the Cys residue is estimated to be 8.58 at 25 degrees C using the statistically weighted free energies of all feasible conformations for the Cys and Cys (-) dipeptides in the gas phase and solvation free energies, which is consistent with the observed values of 8.3 and 8.22 +/- 0.16.     

Covalent Scrambling in Porous Polyarylthioethers through a Stepwise SNAr for Tunable Bandgap and Porosity

Porous poly(aryl thioether)s offer stability and electronic tunability by robust sulfur-aryl conjugated architecture, but synthetic access is hindered due to limited control over the nucleophilic nature of sulfides and the air sensitivity of aromatic thiols. Here, we report a simple, one-pot, inexpensive, regioselective synthesis of highly porous poly(aryl thioether)s through polycondensation of perfluoroaromatic compounds with sodium sulfide. The unprecedented temperature-dependent para-directing formation of thioether linkages leads to a stepwise transition of the polymer extension into a network, thereby allowing fine control of the porosity and optical band gaps. The obtained porous organic polymers with ultra-microporosity (<1 nm) and sulfur as the surface functional groups show size-dependent separation of organic micropollutants and selective removal of mercury ions from water. Our findings offer easy access to poly(aryl thioether)s with accessible sulfur functionalities and higher complexity, which will help in realizing advanced synthetic designs in applications such as adsorption, (photo)catalysis, and (opto)electronics.     

Proteomics-Based Discovery of First-in-Class Chemical Probes for Programmed Cell Death Protein 2 (PDCD2)

Chemical probes are essential tools for understanding biological systems and for credentialing potential biomedical targets. Programmed cell death 2 (PDCD2) is a member of the B-cell lymphoma 2 (Bcl-2) family of proteins, which are critical regulators of apoptosis. Here we report the discovery and characterization of 10 e , a first-in-class small molecule degrader of PDCD2. We discovered this PDCD2 degrader by serendipity using a chemical proteomics approach, in contrast to the conventional approach for making bivalent degraders starting from a known binding ligand targeting the protein of interest. Using 10 e as a pharmacological probe, we demonstrate that PDCD2 functions as a critical regulator of cell growth by modulating the progression of the cell cycle in T lymphoblasts. Our work provides a useful pharmacological probe for investigating PDCD2 function and highlights the use of chemical proteomics to discover selective small molecule degraders of unanticipated targets.     

Scaling laws for the photoionization cross section of two-electron atoms

The cross sections for single-electron photoionization in two-electron atoms show fluctuations which decrease in amplitude when approaching the double-ionization threshold. Based on semiclassical closed orbit theory, we show that the algebraic decay of the fluctuations can be characterized in terms of a threshold law sigma proportional to |E|(mu) as E --> 0(-) with exponent mu obtained as a combination of stability exponents of the triple-collision singularity. It differs from Wannier's exponent dominating double-ionization processes. The details of the fluctuations are linked to a set of infinitely unstable classical orbits starting and ending in the nonregularizable triple collision. The findings are compared with quantum calculations for a model system, namely, collinear helium.     

In-Depth TEM Investigation on Structural Inhomogeneity within a Primary LixNi0.835Co0.15Al0.015O2 Particle: Origin of Capacity Decay during High-Rate Discharge

The structural stability of cathode materials during electrochemical reactions, in particular, under high-rate discharge, is pertinent to the design and development of new electrode materials. This study investigates the structural inhomogeneity that develops within a single LiNi_0.835Co_0.15Al_0.015O₂ (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8 V) developed surface areas in which the layered structure was recovered, although the interiors retained the degraded spinel structure. These micro- and nano-scale structural inversions from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni-rich cathode materials.     

On the beam transport of a helical coaxial wiggler for a free-electron laser

Dynamics of an electron beam in a helical coaxial wiggler is studied. It is observed that the electrons perform betatron oscillation in a potential well that reflects the effective radiation pressure of the wiggler field and a centrifugal force due to an average azimuthal drift.     

Refrigerant distribution in a parallel flow heat exchanger having vertical headers and heated horizontal tubes

Refrigerant R-410a flow distribution is experimentally studied in a test section simulating a parallel flow heat exchanger having vertical headers with two pass configuration. Tubes are heated to yield a test section outlet superheat of 5 °C with inlet quality of 0.3. Mass flux is varied from 50 kg/m² s to 70 kg/m² s. Effects of inlet and outlet locations are investigated in a search for an optimum configuration. Results show that, significant liquid flows through bottom channels, and less liquid is supplied to top channels. As for the inlet location, better flow distribution (pressure drop as well) is obtained for top inlet as compared with middle inlet. As for the outlet location, top or bottom outlet is better than middle outlet. Correlations are developed for the fraction of liquid or gas taken off by downstream channel as a function of header gas Reynolds number at immediate upstream. The correlations may be used to predict the liquid or gas distribution in a parallel flow heat exchanger having vertical headers. A novel thermal performance evaluation method, which accounts for tube-side flow mal-distribution is proposed.