The hydrophobicity profiles across phosphatidylcholine (PC)-cholesterol bilayer membranes were estimated in both frozen liposome suspensions and fluid-phase membranes as a function of alkyl chain length, unsaturation, and cholesterol mole fraction. A series of stearic acid spin labels, with the probe attached to various positions along the alkyl chain, cholesterol-type spin labels (cholestane and androstane spin labels), and Tempo-PC were used to examine depth-dependent changes in local hydrophobicity, which is determined by the extent of water penetration into the membrane. Local hydrophobicity was monitored primarily by observing the z component of the hyperfine interaction tensor (Az) of the nitroxide spin probe in a frozen suspension of the membrane at -150 degrees C and was further confirmed in the fluid phase by observing the rate of collision of Fe(CN)6(3-) with the spin probe in the membrane using saturation recovery ESR. Saturated-PC membranes show low hydrophobicity (high polarity) across the membrane, comparable to 2-propanol and 1-octanol, even at the membrane center where hydrophobicity is highest. Longer alkyl chains only make the central hydrophobic regions wider without increasing the level of hydrophobicity. Introduction of a double bond at C9-C10 decreases the level of water penetration at all locations in the membrane, and this effect is considerably greater than the cis configuration than with the trans configuration. Incorporation of cholesterol (30 mol %) dramatically changes the profiles; it decreases hydrophobicity (increases water penetration) from the polar headgroup region to a depth of approximately C7 and C9 for saturated- and unsaturated-PC membranes, respectively, which is about where the bulky rigid steroid ring structure of cholesterol reaches in the membrane. Membrane hydrophobicity sharply increases at these positions from the level of methanol to the level of pure hexane, and hydrophobicity is constant in the inner region of the membrane. Thus, formation of effective hydrophobic barriers to permeation of small polar molecules requires alkyl chain unsaturation and/or cholesterol. The thickness of this rectangular hydrophobic barrier is less than 50% of the thickness of the hydrocarbon regions. Results obtained in dioleoyl-PC-cholesterol membranes in the fluid phase are similar to those obtained in frozen membranes. These results correlate well with permeability data for water and amino acids in the literature.
Membranes made of dimyristoylphosphatidylcholine and cholesterol, one of the simplest paradigms for the study of liquid ordered-disordered phase separation, were investigated using a pulse-EPR spin-labeling method in which bimolecular collision of molecular oxygen with the nitroxide spin label is measured. This method allowed discrimination of liquid-ordered, liquid-disordered, and solid-ordered domains because the collision rates (OTP) differ in these domains. Furthermore, the oxygen transport parameter (OTP) profile across the bilayer provides unique information about the three-dimensional dynamic organization of the membrane domains. First, the OTP in the bilayer center in the liquid-ordered domain was comparable to that in the liquid-disordered domain without cholesterol, but the OTP near the membrane surface (up to carbon 9) was substantially smaller in the ordered domain, i.e., the cholesterol-based liquid-ordered domain is ordered only near the membrane surface, still retaining high levels of disorder in the bilayer center. This property may facilitate lateral mobility in ordered domains. Second, in the liquid-disordered domain, the domains with approximately 5 mol % cholesterol exhibited higher OTP than those without cholesterol, everywhere across the membrane. Third, the transmembrane OTP profile in the liquid-ordered domain that contained 50 mol % cholesterol dramatically differed from that which contained 27 mol % cholesterol.
The field of flexible antennas is witnessing an exponential growth due to the demand for wearable devices, Internet of Things (IoT) framework, point of care devices, personalized medicine platform, 5G technology, wireless sensor networks, and communication devices with a smaller form factor to name a few. The choice of non-rigid antennas is application specific and depends on the type of substrate, materials used, processing techniques, antenna performance, and the surrounding environment. There are numerous design innovations, new materials and material properties, intriguing fabrication methods, and niche applications. This review article focuses on the need for flexible antennas, materials, and processes used for fabricating the antennas, various material properties influencing antenna performance, and specific biomedical applications accompanied by the design considerations. After a comprehensive treatment of the above-mentioned topics, the article will focus on inherent challenges and future prospects of flexible antennas. Finally, an insight into the application of flexible antenna on future wireless solutions is discussed.
Direct evidence for the existence of an acoustic cutoff frequency in the solar atmosphere is given by observations performed by using the HELioseismological Large Regions Interferometric DEvice operating on the Vacuum Tower Telescope located on Tenerife. The observational results demonstrate variations of the cutoff with atmospheric heights. The observed variations of the cutoff are compared to theoretical predictions made by using five acoustic cutoff frequencies that have been commonly used in helioseismology and asteroseismology. The comparison shows that none of the theoretical predictions is fully consistent with the observational data. The implication of this finding is far reaching as it urgently requires either major revisions of the existing methods of finding acoustic cutoff frequencies or developing new methods that would much better account for the physical picture underlying the concept of cutoff frequencies in inhomogeneous media.
The value of Az (z-component of the hyperfine interaction tensor) obtained directly from X-band EPR spectra of stearic acid spin labels and tempocholine dipalmitoylphosphatidic acid ester in frozen suspension of phosphatidylcholine (PC) membranes has been used as a hydrophobicity parameter. Using probes with the nitroxide moiety at various depths in the membrane, the shape of the hydrophobic barrier, which is determined by the extent of water penetration into the membrane, has been estimated. Incorporation of 10 mol% polar carotenoids, zeaxanthin, violaxanthin, or lutein into the saturated PC bilayer significantly increases the hydrophobicity of the membrane interior but decreases hydrophobicity (increases water penetration) in the polar headgroup region. Hydrophobicity at the membrane center increases from the level of propanolpentanol, which have dielectric constants of 10-20, to the level of dipropylamine, with a dielectric constant close to 3. Longer alkyl chains decrease the effect of polar carotenoids in the polar headgroup region, but not in the central hydrophobic region. In an unsaturated egg yolk PC membrane, polar carotenoids were found to increase the hydrophobicity of the membrane interior to a higher level than in saturated PC membranes. At the membrane center hydrophobicity reaches the level close to pure hexane (epsilon approximately 2). The above results were confirmed by studying accessibility of Fe(CN)6(3-) ion dissolved in water into dimyristoyl-PC-lutein membranes at 30 degrees C. Obtained hydrophobicity profiles correlate well with permeability data for water in the literature.
Electron paramagnetic resonance (EPR) spin-labeling methods were used to study the effects of carotenoids on the physical properties of saturated phosphatidylcholine (PC) membranes to evaluate the contribution of the terminal hydroxyl groups of xanthophyll molecules to the carotenoid-membrane interaction. Effects of the dipolar, terminally dihydroxylated carotenoid lutein on membrane phase transition, fluidity, order, and polarity were compared with those of monopolar (beta-cryptoxanthin) and nonpolar (beta-carotene) carotenoids. These effects were monitored at the membrane center as a function of the amount of the carotenoid added to the sample and as a function of temperature for fluid-phase membranes. PC membranes with different thickness (from 12 to 22 carbons in alkyl chains) were used. Carotenoids shifted to lower temperatures and broadened the main phase transition of PC membranes. They decreased the membrane fluidity and increased the order of alkyl chains. Carotenoids also increased the hydrophobicity of the membrane interior. These effects were the strongest for lutein, significantly weaker for beta-cryptoxanthin, and negligible for beta-carotene. They decreased with the increase of the membrane thickness. Presented results suggest that anchoring of carotenoid molecules at the opposite membrane surfaces by polar hydroxyl groups is significant in enhancing their effects on membrane properties. This manuscript also shows the ability of EPR spin-labeling methods to monitor different membrane properties that can be applied in biotechnological studies with the use of liposomes.
The discrimination by oxygen transport (DOT) method is a dual-probe saturation-recovery electron paramagnetic resonance approach in which the observable parameter is the spin-lattice relaxation time (T1) of lipid spin labels, and the measured value is the bimolecular collision rate between molecular oxygen and the nitroxide moiety of spin labels. This method has proven to be extremely sensitive to changes in the local oxygen diffusion-concentration product (around the nitroxide moiety) because of the long T1 of lipid spin labels (1-10 micros) and also because molecular oxygen is a unique probe molecule. Molecular oxygen is paramagnetic, small, and has the appropriate level of hydrophobicity that allows it to partition into various supramolecular structures such as different membrane domains. When located in two different membrane domains, the spin label alone most often cannot differentiate between these domains, giving very similar (indistinguishable) conventional electron paramagnetic resonance spectra and similar T1 values. However, even small differences in lipid packing in these domains will affect oxygen partitioning and oxygen diffusion, which can be easily detected by observing the different T1s from spin labels in these two locations in the presence of molecular oxygen. The DOT method allows one not only to distinguish between the different domains, but also to obtain the value of the oxygen diffusion-concentration product in these domains, which is a useful physical characteristic of the organization of lipids in domains. Profiles of the oxygen diffusion-concentration product (the oxygen transport parameter) in coexisting domains can be obtained in situ without the need for the physical separation of the two domains. Furthermore, under optimal conditions, the exchange rate of spin-labeled molecules between the two domains could be measured.
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