Lithium garnet based free-standing solid polymer composite membrane for rechargeable lithium battery

Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (W_avg ~?5?×?10⁶) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO₄) and lithium garnet oxide Li_6.28Al_0.24La₃Zr₂O₁₂ (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li⁺ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li⁺ conductivity of 4.40?×?10^?4 S cm^?1 and wide electrochemical window (4.5 V) is observed for PEO₈/LiClO₄?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO₂ as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g^?1/142 mAh g^?1 at 25 °C with 0.06 C-rate.     

Self-assembled hybrid polymer-TiO2 nanotube array heterojunction solar cells

Films comprised of 4 microm long titanium dioxide nanotube arrays were fabricated by anodizing Ti foils in an ethylene glycol based electrolyte. A carboxylated polythiophene derivative was self-assembled onto the TiO2 nanotube arrays by immersing them in a solution of the polymer. The binding sites of the carboxylate moiety along the polymer chain provide multiple anchoring sites to the substrate, making for a stable rugged film. Backside illuminated liquid junction solar cells based on TiO2 nanotube films sensitized by the self-assembled polymeric layer showed a short-circuit current density of 5.5 mA cm-2, a 0.7 V open circuit potential, and a 0.55 fill factor yielding power conversion efficiencies of 2.1% under AM 1.5 sun. A backside illuminated single heterojunction solid state solar cell using the same self-assembled polymer was demonstrated and yielded a photocurrent density as high as 2.0 mA cm-2. When a double heterojunction was formed by infiltrating a blend of poly(3-hexylthiophene) (P3HT) and C60-methanofullerene into the self-assembled polymer coated nanotube arrays, a photocurrent as high as 6.5 mA cm-2 was obtained under AM 1.5 sun with a corresponding efficiency of 1%. The photocurrent action spectra showed a maximum incident photon-to-electron conversion efficiency (IPCE) of 53% for the liquid junction cells and 25% for the single heterojunction solid state solar cells.     

Synthesis of poly(urethane‐imide) using aromatic secondary amine‐blocked polyurethane prepolymer

A set of poly(urethane‐imide)s were prepared using blocked Polyurethane (PU) prepolymer and pyromellitic dianhydride (PMDA). The PU prepolymer was prepared by the reaction of polyether glycol and 2,4‐tolylene diisocyanate, and end capped with N‐methyl aniline. The PU prepolymer was reacted with PMDA until the evolution of carbon dioxide ceased. The effect of tertiary amine catalysts, organo tin catalysts, solvents, and reaction temperature were studied and compared with the poly(urethane‐imide) prepared using phenol‐blocked PU prepolymer. N‐methyl aniline blocked PU prepolymer gave a higher molecular weight poly(urethane‐imide) at a lower reaction temperature in a shorter time. Amine catalysts were found to be more efficient than organo tin catalysts. The reaction was favorable in particular with N‐ethylmorpholine and diazabicyclo(2.2.2)octane (DABCO) as catalysts, and dimethylpropylene urea as a reaction medium. The poly(urethane‐imide)s were characterized by FTIR, GPC, TGA, and DSC analyses. The molecular weight decreased with an increase in reaction temperature. The thermal stability of the PU was found to increase by the introduction of imide component. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4032–4037, 2000     

Self‐Healing Colloidal Crystals

Healing hands : A complex interplay between colloidal and polymeric energetics in microgel self‐assembly behavior results in soft colloidal assemblies with self‐healing properties. Repulsive soft spheres can adopt highly compressed conformations in colloidal crystalline lattices without directly contacting the nearest neighbors (see picture). This distant action is directly responsible for the self‐healing of the assemblies.

     

Chern–Simons classes for a superconnection

In this note we define the Chern–Simons classes of a flat superconnection, D+L$D+L$, on a complex Z/2Z$\mathbb{Z}/2\mathbb{Z}$-graded vector bundle E$E$ on a manifold such that D$D$ preserves the grading and L$L$ is an odd endomorphism of E$E$. As an application, we obtain a definition of Chern–Simons classes of a (not necessarily flat) morphism between flat vector bundles on a smooth manifold. An application of Reznikov's theorem shows the triviality of these classes when the manifold is a compact Kähler manifold or a smooth complex quasi-projective variety in degrees >1$>1$.     

Unraveling the aflatoxin-FAPY conundrum: structural basis for differential replicative processing of isomeric forms of the formamidopyrimidine-type DNA adduct of aflatoxin B1

Aflatoxin B1 (AFB) epoxide forms an unstable N7 guanine adduct in DNA. The adduct undergoes base-catalyzed ring opening to give a highly persistent formamidopyrimidine (FAPY) adduct which exists as a mixture of forms. Acid hydrolysis of the FAPY adduct gives the FAPY base which exists in two separable but interconvertible forms that have been assigned by various workers as functional, positional, or conformational isomers. Recently, this structural question became important when one of the two major FAPY species in DNA was found to be potently mutagenic and the other a block to replication [Smela, M. E.; Hamm, M. L.; Henderson, P. T.; Harris, C. M.; Harris, T. M.; Essigmann, J. M. Proc. Natl. Acad. Sci. U.S.A. 2002, 99, 6655-6660]. NMR studies carried out on the AFB-FAPY bases and deoxynucleoside 3',5'-dibutyrates now establish that the separable FAPY bases and nucleosides are diastereomeric N5 formyl derivatives involving axial asymmetry around the congested pyrimidine C5-N5 bond. Anomerization of the protected beta-deoxyriboside was not observed, but in the absence of acyl protection, both anomerization and furanosyl --> pyranosyl ring expansion occurred. In oligodeoxynucleotides, two equilibrating FAPY species, separable by HPLC, are assigned as anomers. The form normally present in duplex DNA is the mutagenic species. It has previously been assigned as the beta anomer by NMR (Mao, H.; Deng, Z. W.; Wang, F.; Harris, T. M.; Stone, M. P. Biochemistry 1998, 37, 4374-4387). In single-stranded environments the dominant species is the beta anomer; it is a block to replication.     

A cationic tetrahedral chromophore for amplified DNA detection

The tetrahedral cationic chromophore, tetrakis [4-(9,9-bis(6′-(N,N,N-trimethylammonium)hexyl)-2-fluorenyl)phenyl]methane (1) shows better fluorescence resonance energy transfer (FRET) to the fluorescein (Fl) attached to the 5′-terminus of double-stranded DNA (dsDNA-Fl) as compared to the linear oligomers 2 and 3 and also provides efficient DNA hybridization detection.     

Effects of target-masker contextual similarity on the multimasker penalty in a three-talker diotic listening task

In many multitalker listening tasks, the degradation in performance that occurs when the number of interfering talkers increases from one to two is much larger than would be predicted from the corresponding decrease in the signal-to-noise ratio (SNR). In this experiment, a variety of contextually-relevant speech maskers, contextually-irrelevant speech maskers and non-speech maskers were used to examine the impact that the characteristics of the interfering sound sources have on the magnitude of this "multimasker penalty." The results show that a significant multimasker penalty only occurred in cases where two specific conditions were met: 1) the stimulus contained at least one contextually-relevant masker that could be confused with the target; and 2) the signal-to-noise ratio of the target relative to the combined masker stimulus was less than 0 dB. Remarkably, in cases where one masker was contextually relevant, the specific characteristics of the second masker had virtually no impact on the size of the multimasker penalty. Indeed, when the results were corrected for random guessing, there was essentially no difference in performance between conditions with three contextually-relevant talkers and those with two contextually-relevant talkers and one irrelevant talker. The results of a second experiment suggest that the listeners are generally able to hear keywords spoken by all three talkers even in situations where the multimasker penalty occurs, implying that the primary cause of the penalty is a degradation in the listener's ability to use prosodic cues and voice characteristics to link together words spoken at different points in the target phrase.     

Rate dependence of human visual cortical response due to brief stimulation: an event-related fMRI study

The human brain response to a wide range of visual stimulus rates presented over a prolonged time period has been investigated by various neuroimaging techniques. However, to date, no imaging study has been performed to study the dynamic human brain response to various stimulus rates when presented in a short time. This report describes activation in the human brain due to brief visual stimulus presentation (1 s) for stimulus rates varying from 1 to 20 Hz using event-related functional MRI (fMRI). Our results show that the amplitude of the fMRI response increases with the stimulus frequency and plateaus at 6 Hz. This finding differs slightly from the results of previous blocked task paradigm experiments (with a longer time of stimulus presentation), in which the response peaks at approximately 8 Hz and then decreases. Our results are in close agreement with previously published psychophysical studies, suggesting that the fMRI signal in this experiment is indicative of cortical activity related to visual processing.     

Electromechanical response of (3–0, 3–1) particulate,fibrous, and porous piezoelectric composites with anisotropic constituents: A model based on the homogenization method

An analytical framework based on the homogenization method has been developed to predict the effective electromechanical properties of periodic, particulate and porous, piezoelectric composites with anisotropic constituents. Expressions are provided for the effective moduli tensors of n-phase composites based on the respective strain and electric field concentration tensors. By taking into account the shape and distribution of the inclusion and by invoking a simple numerical procedure, solutions for the electromechanical properties of a general anisotropic inclusion in an anisotropic matrix are obtained. While analytical forms are provided for predicting the electroelastic moduli of composites with spherical and cylindrical inclusions, numerical evaluation of integrals over the composite microstructure is required in order to obtain the corresponding expressions for a general ellipsoidal particle in a piezoelectric matrix. The electroelastic moduli of piezoelectric composites predicted by the analytical model developed in the present study demonstrate excellent agreement with results obtained from three-dimensional finite-element models for several piezoelectric systems that exhibit varying degrees of elastic anisotropy.