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Jan 15, - Igor Kuvychko received his M. Introduction 2. Synthesis 3. Intra- and Intermolecular Arrangements of Bola Headgroups 3. Crystal Structures 3.
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Na and I. Download as PDF or read Sempre que ouvimos a palavra interface nos remetemos a tecnologia. Portable document format PDF The most tightly bound dyes are those with a hydrophobic core and two hydrophilic end groups or, in other words, bola dyes. The GIXD studies show the self-assembly of a bimetallic film, where the long molecules are arranged head-to-head intercalating the two different ions in an alternating manner Figure 27b.
Up bilayers were thus assembled.
The alternating adsorption procedure was also followed by quartz balance measurements. Polydi- Fuhrhop and Wang Figure The multilayer becomes dichroitic as suggested by the model given. If the dyes, in particular Congo Red, were adsorbed from more dilute solutions Bolaamphiphiles ticular, they often show well-defined distances between the headgroups, which is not the case in SAMs.
Some photoreactive dicationic bolas contained a diazo dye in the center. The azobenzene units underwent cis-trans isomerization upon UV irradiation, and optical dichroism was induced if linearly polarized light was used.
The speed of writing strongly depended on the ionic strength of the medium Figure A comparison of diazo dye bolas of different molecular lengths showed that anionic dye-polycation pairs containing the longest dye, namely, Direct Red 80, underwent a pronounced photoalignment upon irradiation with linearly polarized UV light.
A tilted J-aggregate was obtained under such irradiation Figure It showed a much lower extinction coefficient than the nonaligned probe. Useful photopatterns or holographic reliefs may be formed by such alignment processes. A significant decrease of lamellar spacing and membrane thickness was observed. This was traced back to a change of membrane thickness. This increased the membrane surface area and lowered the interlamellar spacing significantly, already at a ratio of one inclusion Figure Utilizable regions for reaction centers in spherical monolayer lipid membranes MLM vesicles.
The membrane is largely oversized with respect to the entrapped water volume blue. Chemical Reviews, , Vol. Monolayer Lipid Membrane MLM Vesicles Solutes in aqueous solutions of bola vesicles may be concentrated in 1 out of 9 distinct regions.
They do not cross the membrane within several hours. Region 9 is the inside water volume and is occupied by electrolytes, if the mixture is sonicated. Regions 2 and 8, the Gouy-Chapman layer, contain the counterions of the headgroup regions 3 and 7.
If the headgroups are charged, very little flip-flop turnovers occur. Regions 4, 5, and 6 dissolve hydrophobic solutes, which usually concentrate at 4, because the alkyl chains are most flexible there Figure The monolayer lipid membrane MLM has, in contrast to bilayer lipid membranes BLM curve b , no distinct melting point curve a in Figure 31 , which renders it heat resistant.
The anionic sulfonate polyelectrolyte, however, produces such an effect with acridine orange inside the vesicle. In spherical MLM vesicles, the size of both headgroups may either be the same or different. Under favorable conditions, two headgroups of different size may assemble selectively on the inner or outer surface of vesicles to form asymmetric MLMs: all the large headgroups then go to the outer surface, whereas all the smaller headgroups occupy the inner surface Figure The large curvature of vesicles leads to quite different outer and inner surfaces areas.
A bola with a large Fuhrhop and Wang Figure A radical with a fluorinated side chain F-TEMPO concentrates outside and is much more rapidly reduced by ascorbic acid in the bulk water phase than the inside analogue with a CH2 n side chain.
Such separation may be proven by either 1H NMR techniques using shift reagents in the bulk water phase or simply the metachromatic effect of surface-adsorbed methylene blue. It forms aggregates only in the presence of polyanions, e.
The quinone-carboxyl bola of Figure 32a has all the quinone on the outer surface. A unique, single-chain hybrid bola was investigated by Hui. Large vesicles with diameters between and nm and a membrane of monolayer thickness were found in TEMs.
Membrane asymmetry is more important because it may allow the localization of electron donor- Bolaamphiphiles Chemical Reviews, , Vol. The hydrophobic fullerene moieties were partly exposed to water.
Scheme 8 Figure In artificial systems bolas may allow photosynthetic processes from Nature to be copied without using membrane proteins. Hydrolyzable peptide bolas are also useful and nontoxic. Nanowells Nanowells are form-stable gaps in rigid lipid monolayers which are bound to smooth solid surfaces or colloidal particles. They were produced by two-step self-assembly procedures: first, a flat porphyrin molecule was bound in an orientation parallel to the surface; second, upright-standing bolas were selfassembled to the remaining free reaction sites of the same surface.
This leads to the formation of nanowells with the shape of a porphyrin and a height corresponding to the bola length. This will, however, only be the case if the hydrophobic bolas are rigid or if they are connected by two hydrogen-bond chains between secondary amide groups.
Long-distance porphyrin heterodimers on silica particles have, for example, been realized. Porphyrin A was first deposited on aminated silica; a diamido bola containing an activated CC double bond followed and was aminated by Michael addition.
Porphyrin B was then attached to the resulting ring of ammonium groups Figure Light-induced energy transfer was found when Figure Models of diamido bola-coated gold particles.
The rigid coating protected the gold from dissolution by sodium cyanide in the bulk solution, even if it contained nanowells with a porphyrin bottom. The bolas are needed to fixate the monolayer on the substrate, e. The gaps can then be seen as simple models for reactive centers on biological protein and membrane surfaces; catalysis and charge separation may be realized here.
The most useful outside headgroup is oligoethylene OEG , which allows one to study the nanowells in water as well as in various organic solvents, e.
Both water- and chloroform-soluble molecules can be used. Rigid monolayers on smooth citrate gold particles provide perfect protection against corrosion by cyanide in the bulk solution. Even nanowells with a porphyrin bottom allow no passage of the cyanide ions to the gold surface Figure Pores for Ion Transport Figure The diameter of the smooth particles was nm; their surface is, on a molecular scale, close to planar.
A nanowell with a porphyrin bottom was thus established. An ammonium ring was assembled by Michael addition of methylamine at the rim of the nanowell.
A second tetraanionic porphyrin was then attached within this ring. Nanowells with oligoethylene glycol OEG headgroups were also built on the smooth surface of aminated silica particles or on old particles.
These particles are soluble, and their nanowells can be filled in water as well as in chloroform. Pores are hydrophilic domains in vesicle membranes. The building blocks are usually bolas as well as edge amphiphiles. The hydrophobic core must be long enough to cross the lipid membrane, with polar headgroups on both ends and to help to enforce a stretched conformation.
The bola core is then made of a macrocycle or of a row of several small cyclic molecules, which contain a polar and a nonpolar edge. Bacteria produce such amphiphiles in the form of protein helices, which will not be discussed here, or in the form of reduced carbohydrates, tetrahydrofuranes, and related oligomers.
In biological cells such edge amphiphiles lead to a breakdown of the membrane potential; they act as killing antibiotics. Synthetic analogues are often made to achieve ion-selective transport. Nanowells and pores thus serve different purposes. Nanowells with hydrophobic walls with or without hydrophilic hooks and a reactive dye bottom are thus useful as organizing matrix for reactive systems.
Pores are more on the disintegrating side of supramolecular chemistry. They abolish the separating Bolaamphiphiles Chemical Reviews, , Vol. Cation transport across lipid membranes is usually studied in planar bilayers across an aperture in a polystyrene barrier between two aqueous salt solutions.
Transmembrane ion currents can be measured then when a potential of about mV is applied. This worked, for example, when a bola-edge-amphiphile was added to a diphytanoyl phosphatidyl choline bilayer.
No continuous current occurred, but step conductance changes consistent with the closing and opening of the pore were observed. Some openings lasted a second or longer; others were much shorter. The pore also showed some selectivity of NaCl over CsCl. Opening and closing of the gap may either be caused by aggregation of the U-shaped molecules in both parts of the monolayer or by side-on dimerization of stretched bolas Figure 38a.
The bolas carried thioacetic acid on one side and thiosuccinic acid or thioglucoside on the other. The acetate-glucose bola, on the other hand, produced regular step conductance of a single channel.
This difference was explained by the spontaneous formation of asymmetric domains in both cases. The less-charged acetate or glucose migrated preferentially through the hydrophobic bilayer, and the more negative side responded to the applied potential. A negative potential would favor anionanion antiparallel alignments of the molecular dipoles of the bolas and the electric field vector and thereby stabilize the domain, whereas a positive potential would destroy it Figure 38b.
This effect was, however, much less pronounced if electroneutral glucose held the molecules together at the inner side of the membrane. One may expect closure rather than opening of pores here. Bis- crown ether bolas were used to release vesicleentrapped 5-carboxyfluorescein. A thioindigo-connected dimer was 10 times more active as a cis-isomer than in the trans-configuration.
Bola-type cholic acid dimer with methoxysubstituted edges was dissolved in a lipid bilayer membrane. It opened potassium channels after the application of a mV voltage.
In general, only metal ions are supposed to flow through pores, not dye molecules. Aggregation-deaggregation processes were postulated, but no additional evidence for such a process was provided. In this case the hydrophilic edge only contained two axial methoxy groups, while a hydrophilic channel across the bilayers was not obvious.
The destabilization by rigid solutes and their fixation by two end groups only rendered the membrane much more vulnerable to such fields Figure This depends on the number of edge amphiphile molecules within one vesicle membrane. Thus far no flexible channel for the passage of dyes has, however, been described. The disruption of fluid bilayers by membranespanning bolas is certainly not equivalent to a hydrated pore.
It might also happen that single-edge amphiphiles provided hydration spheres on their surface, which allowed temporary ion transport on their surface.
The only experimental proof for an ion pore, which provides an ion channel, consists of the reversible opening and closing of such pores with chemical Figure Addition of EDTA to the bulk aqueous medium reverses the effect; Taurine seals the pore for ion transport. They have been irreversibly sealed by a dicationic bola. Changes of potentials and geometries along the surface of single molecules may just help sliding along polar surfaces.
In protein-based pores, chemical stoppers are well known and act as poisons. Curare and tetradotoxin are prominent examples for cationic Bolaamphiphiles Chemical Reviews, , Vol. Spermine with adamantane substituents and sulfonate headgroups acted as a permanent harpoon. In artificial systems, only one example is known. If a cyclic oligoamine with a hydrophobic edge and two carboxylate end groups was integrated into a monolayer lipid membrane vesicle, the membrane became permeable for iron II ions, which quenched the fluorescence of calcein, which was entrapped with the vesicles water volume.
EDTA could not pass this noncovalent pore either because it was too large or because it was tightly bound to the oligoamine. The calcein fluorescence was restored.
This cycle could be repeated several times and stopped at once when an anionic stopper, e. This system involves, however, no bilayer membrane. Similar results have been reported for anionic monensin derivatives in MLM vesicles, which were closed by a dicationic bola. Fluid lipid membranes also act as barriers for proton transport. A gradient of one pH unit is stable for several hours around neutral pH. Addition of membrane-spanning oligoamines or amides with bulky substituents led to a rapid breakdown of such gradients if it was held by two terminal sulfonate groups Figure The presence of water channels in membranes cannot be proven by the detection of statistical current fluctuations and voltage effects.
Steroidal and crown-ether bolas also produce channels, which could not be closed.
Light-induced charge separation was observed between a quinone bola entrapped in a bilayer vesicle membrane and a zinc porphyrinate in bulk solution. Recombination of charges was, however, as fast as the separation. Electron Conductors Mono- and bilayer lipid membranes of fluid vesicles are perfect insulators with respect to electron transport.