Cathode catalysts degradation mechanism from liquid electrolyte to membrane electrode assembly

Single-cell and half-cell degradation test procedures were evaluated for carbon-supported Pt/C, PtCo/C and PtNi/C catalysts. Half-cell analyses were employed to understand the effect of the number of cycles and of the scan rate over the cathode catalysts degradation under potential cycling from 0.6 to 1.2 V. The data suggested a time-dependent degradation for all three catalytic systems. Single-cell measurements were used to evaluate the impact of catalyst degradation on fuel cell performance. The measurements in both setups showed similar ECSA and ORR mass activity losses. Specific degradation mechanisms related to Pt dissolution, Pt agglomeration, and transitional metal leaching were quantified and correlated with performance losses.     

Improved Stabilities of Labeling Probes for the Selective Modification of Endogenous Proteins in Living Cells and In Vivo

To date, various affinity-based protein labeling probes have been developed and applied in biological research to modify endogenous proteins in cell lysates and on the cell surface. However, the reactive groups on the labeling probes are also the cause of probe instability and nonselective labeling in a more complex environment, e. g., intracellular and in vivo. Here, we show that labeling probes composed of a sterically stabilized difluorophenyl pivalate can achieve efficient and selective labeling of endogenous proteins on the cell surface, inside living cells and in vivo. As compared with the existing protein labeling probes, probes with the difluorophenyl pivalate exhibit several advantages, including long-term stability in stock solutions, resistance to enzymatic hydrolysis and can be customized easily with diverse fluorophores and protein ligands. With this probe design, endogenous hypoxia biomarker in living cells and nude mice were successfully labeled and validated by in vivo, ex vivo, and immunohistochemistry imaging.     

Trehalose-protected lipid membranes for determining membrane protein structure and insertion

Trehalose preserves lipid bilayers during dehydration and rehydration by replacing water to form hydrogen bonds between its own OH groups and lipid headgroups. We compare the lipid conformation and dynamics between trehalose-protected lyophilized membranes and hydrated membranes, to assess the suitability of the trehalose-containing membrane as a matrix for membrane protein structure determination. (31)P spectra indicate that the lipid headgroup of trehalose-protected dry POPC membrane (TRE-POPC) have an effective phase transition temperature that is approximately 50K higher than that of the hydrated POPC membrane. In contrast, the acyl chains have similar transition temperatures in the two membranes. Intramolecular lipid (13)C'-(31)P distances are the same in TRE-POPC and crystalline POPC, indicating that the lipid headgroup and glycerol backbone conformation is unaffected by trehalose incorporation. Intermolecular (13)C-(31)P distances between a membrane peptide and the lipid headgroups are 10% longer in the hydrated membrane at 226 K than in the trehalose-protected dry membrane at 253 K. This is attributed to residual motions in the hydrated membrane, manifested by the reduced (31)P chemical shift anisotropy, even at the low temperature of 226 K. Thus, trehalose lyoprotection facilitates the study of membrane protein structure by allowing experiments to be conducted at higher temperatures than possible with the hydrated membranes.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 25: Mechanisms of aldehyde and carboxylic acid formation

Aldehydes and acids can be formed in numerous reactions in oxidizing polyethylene melts. Significant amounts of aldehydes result from β-scission of alkoxy radicals that are formed on bimolecular hydroperoxide decomposition. There are also large amounts of aldehydes expected from acid-catalyzed decomposition of allylic hydroperoxides as soon as enough acids have accumulated for efficient catalysis. There are difficulties in explaining the formation of aldehydes at a constant rate in sufficient amount for explaining the experimental data. There are much less difficulties with the constant rate of carboxylic acid formation. The α,γ-keto-hydroperoxides that are formed on chain propagation might account for the bulk of the acids formed at a constant rate.The foremost problems with the acids pertain to their formation at increasing rates in the initial as well as in the advanced stages. Formation and decomposition of α,β-di-hydroperoxides and α,γ-di-hydroperoxides is a possibility in this respect. Similarly, α,β-keto-hydroperoxides might be formed on peroxidation in the α-position to ketone groups in the advanced stages. There are considerable difficulties in elucidating the exact role of the aldehydes that are usually seen as the main precursors of the acids. Although there are many possibilities for transformation of aldehydes into acids, the free radical mechanisms envisaged usually have considerable disadvantages. These disadvantages result essentially from fast decarbonylation of acyl radicals and even faster decarboxylation of acyl-oxy radicals. Direct transformation of peracids into acids on reaction with double bonds is always a possibility. Moreover, in the low temperature range (150-160 °C) where hydroperoxides are accumulating, direct reaction of aldehydes with primary and/or secondary hydroperoxides will also yield acids.     

聚乙二醇类表面活性剂对硅表面无电沉积Ag膜光滑作用研究

应用原子力显微镜技术及开路电位～时间谱技术,研究了非离子表面活性剂聚乙二醇2000,6000,20000对硅(100)表面无电沉积银膜的光滑作用.实验表明硅(100)表面无电沉积银的光滑程度以及镀层的质量均随聚乙二醇聚合度的增加而变好.     

Structural investigation on PEO-based polymer electrolytes dispersed with Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

Thin solid polymer electrolytes based on polyethylene oxide (PEO) and silver triflate (AgCF₃SO₃) dispersed with various concentrations of aluminum oxide (Al₂O₃) nanoparticles have been prepared by solution casting technique. These thin polymer films are found to have thickness of the order of 30 to 100 μm. The X-ray diffraction (XRD) patterns have indicated the amorphous nature of the polymer electrolyte. The differential scanning calorimeter (DSC) traces showed slight change in the glass transition temperature (T _g) whereas the degree of crystallization (X _c) decreases markedly due to the addition of alumina nanoparticles. Fourier transform infrared (FTIR) spectral analysis of all these samples has revealed the presence of absorption bands around 1,000 cm⁻¹; thus indicating the complexation of silver ions with oxygen in PEO. Employing the Wagner’s polarization technique as the standard method, the total ionic transference number for the complexed polymer electrolyte was found to be approximately unity thereby revealing that the significant contribution to electrical conduction was due to ions only. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006     

Membrane fluidity altering and enzyme inactivating in sarcoma 180 cells post the exposure to sonoactivated hematoporphyrin in vitro

Sonodynamic therapy (SDT) is a novel tumor therapy method. We investigated membrane fluidity, activity of the enzymes and membrane morphology in vitro post hematoporphyrin-SDT treatment. Furthermore, the potential mechanisms behind the changes in membrane fluidity and enzymic activity were discussed. Tumor cells were exposed to ultrasound at 1.75 MHz for up to 3 min in the presence and absence of hematoporphyrin. Fluorescence polarization, contents of Malonaldehyde, and levels of free fatty acid were assessed. Activity of enzymes was checked by the plumbic nitrate detection method. For the morphologic study, a scanning electron microscope was used to observe the cellular surface. Ultrasonically induced cell damage increased in the presence of HPD (from 15% to 24%). Compared with ultrasound treatment alone, the fluidity decreased from 5.037 to 3.908, malonaldehyde content and free fatty acid level increased from 0.743 nmol/mL to 0.979 nmol/mL and from 237.180 μmol/L to 730.769 μmol/L, respectively, post ultrasound combined with HPD treatment. Inactivity of adenylate cyclase and guanylate cyclase and significant deformation of the cellular surface were also observed post SDT treatment. Our results suggested that alterations in membrane modality and lipid composition played important roles in SDT-mediated inhibition of tumor growth, even inducing tumor cell death, which might be attributed to a sono-chemical activation mechanism.     

Electrolyte interaction with DPPC vesicles: An ESR study

Summary The partition of the spin probe TEMPO between the fluid lipid phase of single-walled vesicles of dipalmitoylphosphatidylcholine and the aqueous bulk solution have been used to investigate the interaction of monovalent ions with polar head of neutral phospholipids. The study has been performed by electron spin resonance (ESR) spectroscopy in the temperature range of (20÷60)°C and in the presence of (0÷3) M 1∶1 electrolyte. In the absence of electrolyte the spin probe TEMPO reveals the characteristic order→disorder DPPC main phase transition atT _m≈37°C, while the pretransition occurs atT _p≈27.5°C. On increasing the ionic strength of the dispersion medium it results for the partition coefficient,P _C, that, at each temperature,P _C(3)>P _C(2)>P _C(1)>P _C(0). Correspondingly, the pretransition disappears and theT _m value downshifts from ≈37°C with 0 M electrolyte to ≈34°C with 3M salt in the order:T _m(3)>T _m(2)>T _m(1)>T _m(0). The results suggest an increase in the net surface charge density of vesicles due to high ionic-strength values. The alteration of the electric interactions occurring into the polar zone of DPPC bilayer reduces the hindrances which, in turn, favour the enhancement of TEMPO partitioning in the hydrophobic core of phospholipid bilayers. The authors of this paper have agreed to not receive the proofs for correction.     

Fluctuation-magnification of non-equilibrium membranes near a wall

Membranes in thermal equilibrium are well known to exhibit Brownian motion type shape fluctuations. Membranes containing active force centers -- such as chemically active membrane proteins -- suffer additional non-equilibrium shape fluctuations due to the activity of these force centers. We demonstrate, using scaling arguments, that non-equilibrium shape fluctuations are in general greatly amplified by the presence of a nearby wall or membrane due to the absence of a fluctuation-dissipation theorem. For adhesive membranes, this fluctuation magnification effect may facilitate the establishment of bonding. For non-adhesive membranes, fluctuation magnification produces a long-range repulsive pressure which can exceed the well known Helfrich repulsion due to purely thermal fluctuations. Received: 1 September 1997 / Accepted: 3 December 1997     

Versatile ferrofluids based on polyethylene glycol coated iron oxide nanoparticles

Versatile ferrofluids based on polyethylene glycol coated iron oxide nanoparticles were obtained by a facile protocol and thoroughly characterized. Superparamagnetic iron oxide nanoparticles synthesized using a modified forced hydrolysis method were functionalized with polyethylene glycol silane (PEG silane), precipitated and dried. These functionalized particles are dispersable in a range of solvents and concentrations depending on the desired properties. Examples of tunable properties are magnetic behavior, optical and magneto-optical response, thermal features and rheological behavior. As such, PEG silane functionalized particles represent a platform for the development of new materials that have broad applicability in e.g. biomedical, industrial or photonic environments. Magnetic, optical, magneto-optical, thermal and rheological properties of several ferrofluids based on PEG coated particles with different concentrations of particles dispersed in low molecular mass polyethylene glycol were investigated, establishing the applicability of such materials.