Prototype cells of the configuration Li/,~SM S as Li2S,, THF, 1M LiAsF6/C have been characterized with regard to capacity, rate, and rechargeability. Virtually 100% of the theoretical capacity could be realized at 50~ at rates below 1.0 mA/cm 2. In high rate cell configurations, 75% cathode utilization is possible at ,-.4 mA/cm 2 (C/3-C/4rate). The capacities at high rate are enhanced by Lewis acids, although the ultimate cause of rate limitation is passivation of the current collector by discharge products. The self-discharge rates of Li in contact with 4-5M S (as Li2Sn) solutions reveal capacity losses of 0.5%/day at 25~ to 4.4%/day at 71~ Based on the experimental results, a practical energy density of ~300 W-hr kg-' is possible using a standard cell design. Results on the battery's rechargeability are briefly reviewed.An ambient temperature Li/S battery utilizing an organic electrolyte has many attractive possibilities, among them high energy density, and the use of relatively low cost, relatively safe materials. Previous attempts to develop such a cell have involved the incorporation of insoluble Ss directly into the current collector (1-3). In general, very poor discharge efficiencies were obtained. One explanation put forth for these results is that some of the Ss was reduced to soluble polysulfide, Sn -2, which "escaped" from the cathode current collector and self-discharged on the Li anode (4). One recent moderately successful approach to increasing the S utilization efficiency was to add a Lewis acid, BF3, supposedly to suppress polysulfide formation (4, 5).The highest rate Li batteries, such as Li/SOC12 (6-8) and Li/SO2 (9, 10), have employed liquid cathodes. Here, very good electrical contact is maintained between the cathode material and the current collector through all phases of discharge. Both Ss and its ultimate discharge product, Li2S, are electrical insulators. Thus, it is likely that insulation of the cathode material, rather than S,~ -~ formation, led to poor results for Li/S cells. In our experience, the reaction between Li and dissolved Sn -2 is very slow, and the formation of dissolved Sn -2 enhances cathode utilization. In this regard, the explanation of the effect of BF8 on sulfur utilization is not very convincing.In contrast to most previous work on Li/S batteries, we have chosen to investigate a system where the S is completely dissolved in the electrolyte, as Li2S~ (11,12). Hence, the theoretical cell reaction becomes
A star polymer composed of amphiphilic block copolymer arms has been synthesized and characterized. The core of the star polymer is polyamidoamine (PAMAM) dendrimer, the inner block in the arm is lipophilic poly(epsilon-caprolactone) (PCL), and the outer block in the arm is hydrophilic poly(ethylene glycol) (PEG). The star-PCL polymer was synthesized first by ring-opening polymerization of epsilon-caprolactone with a PAMAM-OH dendrimer as initiator. The PEG polymer was then attached to the PCL terminus by an ester-forming reaction. Characterization with SEC, (1)H NMR, FTIR, TGA, and DSC confirmed the star structure of the polymers. The micelle formation of the star copolymer (star-PCL-PEG) was studied by fluorescence spectroscopy. Hydrophobic dyes and drugs can be encapsulated in the micelles. A loading capacity of up to 22% (w/w) was achieved with etoposide, a hydrophobic anticancer drug. A cytotoxicity assay demonstrated that the star-PCL-PEG copolymer is nontoxic in cell culture. This type of block copolymer can be used as a drug delivery carrier.
Iridium oxide films formed by electrodeposition onto noniridium metal substrates are compared with activated iridium oxide films (AIROFs) as a low impedance, high charge capacity coating for neural stimulation and recording electrodes. The electrodeposited iridium oxide films (EIROFs) were deposited on Au, Pt, PtIr, and 316 LVM stainless steel substrates from a solution of IrCl4, oxalic acid, and K2CO3. A deposition protocol involving 50 potential sweeps at 50 mV/s between limits of 0.0 V and 0.55 V (versus Ag AgCl) followed by potential pulsing between the same limits produced adherent films with a charge storage capacity of >25 mC/cm2. Characterization by cyclic voltammetry and impedance spectroscopy revealed no differences in the electrochemical behavior of EIROF on non-Ir substrates and AIROF. The mechanical stability of the oxides was evaluated by ultrasonication in distilled water followed by dehydration and rehydration. Stability under charge injection was evaluated using 200 micros, 5.9 A/cm2 (1.2 mC/cm2) cathodal pulses. Loss of iridium oxide charge capacity was comparable for AIROFs and the EIROFs, ranging from 1% to 8% of the capacity immediately after activation or deposition. The EIROFs were deposited and evaluated on silicon microprobe electrodes and on metallized polyimide electrodes being developed for neural recording and stimulation applications.
Electrochemical and spectroscopic measurements were used to characterize the electrochromic behavior of sputtered V 20 5 films. In response to lithium intercalation, the fundamental optical absorption edge of V 20 5 shifts to high energies by 0.20-0.31 eV as the lithium concentration increases from Li o . o V 20 5 to Lio.86 V 20S' There is a corresponding increase in the near-infrared absorption that exhibits Beer's law behavior at low lithium concentrations. The shift in absorption edge results in a large decrease in absorbance in the 350-4:50 nm wavelength range. This effect is most prevalent in thin films which exhibit a yel10w to colorless optical modulation on lithium intercalation. The cathodic coloration in the near infrared is relatively weak with a maximum coloration efficiency of 35 cm 2 /C [This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP: 137.
Increased activity of the epithelial sodium channel (ENaC) in the respiratory airways contributes to the pathophysiology of cystic fibrosis (CF), a genetic disease caused by mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) gene. In some patients suffering from atypical CF a mutation can be identified in only one CFTR allele. We recently identified in this group of CF patients a heterozygous mutation (W493R) in the α-subunit of ENaC. Here, we investigate the functional effects of this mutation by expressing wild-type αβγENaC or mutant α W493R βγENaC in Xenopus oocytes. The αW493R mutation stimulated amiloride-sensitive whole-cell currents ( I ami ) by ∼4-fold without altering the single-channel conductance or surface expression of ENaC. As these data suggest that the open probability (P o ) of the mutant channel is increased, we investigated the proteolytic activation of ENaC by chymotrypsin. Single-channel recordings revealed that chymotrypsin activated near-silent channels in outside-out membrane patches from oocytes expressing wild-type ENaC, but not in membrane patches from oocytes expressing the mutant channel. In addition, the αW493R mutation abolished Na + self inhibition of ENaC, which might also contribute to its gain-of-function effects. We conclude that the αW493R mutation promotes constitutive activation of ENaC by reducing the inhibitory effect of extracellular Na + and decreasing the pool of near-silent channels. The resulting gain-of-function phenotype of the mutant channel might contribute to the pathophysiology of CF in patients carrying this mutation.
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