Giant vesicle formation through self-assembly of chitooligosaccharide-based graft copolymers.

A simple approach is described for the preparation of chitooligosaccharide-based giant vesicles with variable size by simply tuning the water content in the water-dioxane mixture, by which reactive vesicles with diameters in the range of 0.5-400 microm were easily prepared.

Hydrophobic and hydrophilic yoctowells.

Rigid molecular monolayers made of alpha,omega-diamido lipids form yoctoliter-sized gaps ("yoctowells", 1 yL = 10(-24) L or 1 nm3) around porphyrin islands on smooth surfaces. Their hydrophobic walls adsorb cyclic edge amphiphiles, e.g., trans-1,2-cyclohexanediol, cellobiose, and tyrosine, which fill-up the wells slowly and irreversibly by a process called "kinetic trapping". Wells with oligoethylene or oligoamide walls are effective as 3D-crown ethers or oligoamide barrels for reversible "thermodynamic trapping" of amines or amides. Three porphyrins A, B, and C were sorted as stacks within the yoctowells, and a methylammonium ring was established at their rim to fixate a fourth molecule D at a longer distance. Yoctowells are easy to prepare, characterize, and modify and provide simple models of biological modules.

Hydrophobic and hydrophilic yoctowells as receptors in water.

Hydrophilic yoctowells (volume = 10-24 L) with OEG walls are introduced, which entrap tobramycin, a tetraamino trisaccharide, in water with a binding constant of 107 M-1 but do not interact with cellobiose. This is in contrast to corresponding hydrophobic yoctowells, which kinetically immobilize cellobiose in water, but do not entrap tobramycin.

Scanning force microscopy of upright-standing, isolated calixarene-porphyrin heterodimers.

A water soluble calixarene[4]arene 1 with four guanidinium substituents on the upper rim and propyl groups below was anchored in the propylamino coating of smooth silica particles, and a tricarboxylate-tripod porphyrin 2 of 2 nm height was attached to these cationic islands. The molecular complex with a height of 3 nm was unequivocally detected on the particles' surface by atomic force microscopy in the tapping mode. Although deposits of 1 (height: 1 nm) and 2 (height: 2 nm) were also evident on the smooth silica particles, 3 nm seems to be the minimal height to identify single objects. The soft surface of the particles not only allowed tight attachment of molecular edge amphiphiles by the hydrophobic effect but also immobilized the particles on the mica surface by amine-silicate interactions.

Counting of labelled tyrosine molecules in hydrophobic yoctolitre wells filled with water.

Time-dependent radioactivity and solid-state 13C-NMR measurements of tyrosine entrapped in water-filled yoctolitre (10(-24) L) wells with hydrophobic walls are reported; the results indicate that such wells induce the formation of quasi solid tyrosine if they are brought in contact with 0.1 M solutions of this edge amphiphile.

Aminoglycoside antibiotics aggregate to form starch-like fibers on negatively charged surfaces and on phage lambda-DNA.

The water-soluble (> 200 mg/mL) antibiotics tobramycin, kanamycin, and neomycin spontaneously produce rigid fibers on negatively charged surfaces (mica, graphite, DNA). Atomic force microscopy showed single strands of tobramycin on mica at pH 7 with a length of several hundred nanometers and a diameter of 0.5 nm and double helices with a diameter of 1.0 nm and a helical pitch of 7 nm. At pH 13 (NaOH) up to 15 microm long, rigid fibers with a uniform height of 2.4 nm and an apparent helical pitch of 30 nm were formed along the sodium silicate channels on the surface of mica. Kanamycin and neomycin behaved similarly. Fibers of similar length and width, but without secondary structure, were obtained from aqueous solutions at pH 7 on amorphous, hydrophilized carbon and characterized by transmission electron microscopy. Overstretched phage lambda-DNA strands with a height of 1.0 nm on mica did not interact with tobramycin coils at pH 7. After treatment with EDTA, however, the height of the magnesium-free lambda-DNA strands grew from 1.0 to 3.8 nm after treatment with tobramycin, which suggests a wrapping by the supramolecular fibers. Such fibers may interact with F-actin fibers in biological cells, which would explain the known aggressiveness of aminoglycosides toward bacterial cell membranes and their ototoxicity.

Slow motion, trapping, and sorting of water- and chloroform-soluble porphyrins in nanowells.

A two-step self-assembly procedure on smooth, aminated silica particles established holey monolayers. At first, single, flat-lying porphyrin tetraamides (A) were bound covalently, followed by the build-up of a rigid monolayer made of diamido bolaamphiphiles (bolas) around the porphyrin islands. "Nanowells" around porphyrin (A) bottoms with a uniform diameter of 2.2 nm and varying depths of 0.6, 1.0, or 1.5 nm depending on the length of the applied bolas were thus obtained. Oligoethylene headgroups solubilized the particles in water, ethanol, and chloroform/ethanol, and two hydrogen bond chains between the secondary amide groups prevented swelling of the monolayer. Manganese(III) porphyrinates (B) migrated from the bulk solution to the bottom of the form-stable nanowells with a speed of about 1 pm/s and were trapped there above porphyrin (A). After isolation of the (A,B) particles by centrifugation or ultrafiltration, the particles were suspended in a chloroform solution of a chlorin (C), which was also fixated irreversibly on the bottom of the nanowells. The nanowells thus contained three different porphyrins A,B,C in a noncovalent stack. The reverse sequence A,C,B was built-up correspondingly, first in chloroform/ethanol, and then in water. The "sorting" of A,B,C and A,C,B systems was characterized by visible spectra, sequence-dependent fluorescence quenching, and cyclic voltammetry of the top component. The molecular sorting method is the first of its kind and should be generally useful for the production of noncovalent reaction systems on any smooth surface.

Irreversible or reversible self-assembly procedures yield robust zirconium (IV)-porpyrinphosphonate cones or microm-long fibers of monomolecular thickness.

Stepwise, irreversible self-assembly of porphyrinphosphonates by zirconium(IV) produces cones of 20 nm height and similar widths. Side-on growth cannot be prevented. Reversible fiber growth without metal ions gave micrometer long fibers on mica of 2 nm width, because charge repulsion allowed only for end-on growth.

Porphyrinphosphonate fibers on mica and molecular rows on graphite.

meso-Tetra(phenyl-p-phosphonate) porphyrin forms rigid and well-separated fibers of monomolecular thickness (2.8 nm) and lengths of several micrometers on mica at pH 13 (octasodium salt). The formation of these fibers could be observed directly by tapping mode scanning force microscopy (SFM) and was induced by capillary forces. Normal height images or images with a topographical inversion were observed depending on the distance of the SFM tip. Amplitude-distance curves indicated that a stable meniscus was formed on hydrophilic surface areas below a tip-sample separation of 20 nm. The meniscus let the original nanorods appear as ditches in the mica surface and enabled rearrangements. A partly protonated form of the same porphyrin (pH 11.5) gave rows of flat-lying porphyrins on graphite, which appear with molecular resolution in SFM images as well as two-dimensional platelets of monomolecular thickness.

Template synthesis of functionalized polystyrene in ordered silicate channels.

A mesostructured nanocomposite was fabricated by using a novel electroactive, polymerizable surfactant as a template in a sol-gel process, and the first example of well-resolved polystyrene with redoxactive functional group synthesized in silicate matrices was provided.

Porphyrin-acetylene-thiophene polymer wires.

5,15-Bis[acetylene-4-(ethylenedioxy)thiophene]-10,20-bis(4-carboxyphenyl)porphyrin was synthesized by a Sonogashira coupling and polymerized to fibres; TEM and AFM images show uniform porphyrin wires with a length of several micrometers and a thickness of less than 4 nm.

Nanowells on silica particles in water containing long-distance porphyrin heterodimers.

Smooth and nonswelling spherical silica particles with a diameter of 100 nm and an aminopropyl coating are soluble in water at pH 11, coagulate quickly at pH 3, and redissolve at pH 9. Electron microscopy as well as visible spectra of covalently attached porphyrins indicate the aggregation state of the particles. Long-chain alpha,omega-dicarboxylic acids with a terminal oligoethyleneglycol (=OEG)-amide group were attached in a second self-assembly step to the remaining amine groups around the porphyrins. Form-stable 2-nm wells were thus obtained and were characterized by fluorescence quenching experiments using the bottom porphyrin as a target. The one-dimensional diffusion of fitting quencher molecules along the 2-nm pathway took several minutes. Porphyrins with a diameter above 2 nm could not enter the form-stable gaps at all. Added tyrosine stuck irreversibly to the walls of the nanowells and prevented the entrance of quencher molecules, the OEG-headgroups fixated 2,6-diaminoanthraquinone. A ring of methylammonium groups was then fixed at the walls of the wells at a distance of 5 or 10 A with respect to the bottom porphyrin. 2,6-Disulfonatoanthraquinone was attached only loosely to this ring, but the exactly fitting manganese(III) meso-(tetraphenyl-4-sulfonato)porphyrinate (Mn(III) TPPS) was tightly bound. Transient fluorescence experiments showed a fast decay time of 0.2 ns for the bottom porphyrin, when the Mn(III) TPPS was fixated at a distance of 5 A. Two different dyes have thus been immobilized at a defined subnanometer distance in an aqueous medium.

Rigid lipid membranes and nanometer clefts: motifs for the creation of molecular landscapes.

Amphiphilic lipids associate in water spontaneously to form micelles, vesicles, monolayers, or biological membranes. These aggregates are soft and their shape can be changed easily. They behave like complex fluids because they are merely held together by weak, nondirected forces. The most important characteristic of these monolayers is their ability to dissolve hydrophobic molecules in the form of freely movable monomers. The fluid molecular layers are not suitable to anchor the components of chain reactions. However, if the alkyl chains are replaced by rigid skeletons or if the head groups are connected through intermolecular interactions, the aggregates become rigid and their fluid solvent character is lost. The construction of chiral surfaces by synkinesis (synthesis of noncovalent compounds) and of enzyme-type surface clefts of defined size can now be carried out by using rigid lipid membranes. Monolayers and nanometer pores on solid substrates attain sharp edges, and upright nanometer columns on smooth surfaces no longer dissipate. Five examples illustrate the advantages of using rigid molecular assemblies: 1) Cationic domains of rigid edge amphiphiles in fluid membranes act as manipulable ion channels. 2) Spherical micelles, micellar helical fibers, and vesicular tubes can be dried and stored as stable material. Molecular landscapes form on smooth surfaces. 3) alpha,omega-Diamide bolaamphiphiles form rigid nanometer-thick walls on smooth surfaces and these barriers cannot be penetrated by amines. Around steroids and porphyrins, they form rigid nanometer clefts whose walls and water-filled centers can be functionalized. 4) The structure of rigid oligophenylene- and quinone monolayers on electrodes can be changed drastically and reversibly by changing the potential. 5) 10(10) Porphyrin cones on a 1-cm2 gold electrode can be controlled individually by AFM- and STM-tips and investigated by electrochemical, photochemical, and mechanical means. In summary, rigid monolayers and bilayers allow the formation of a great variety of membrane structures that cannot be obtained from classical fluid alkyl amphiphiles.

Manganese Porphyrin Heterodimers and -trimers in Aqueous Solution.

Noncovalent face-to-face heterodimers and -trimers between beta-tetracationic and meso-tetraanionic manganese(III) porphyrins have been prepared in bulk water at pH 12. They are held together by Coulomb interactions between four beta-methylpyridinium and meso-phenylsulfonate or meso-phenylcarboxylate ion pairs in eclipsed orientations. Spectroelectrochemistry has been used to characterize the redox products and to establish reversibility. UV-visible titrations indicate quantitative trimerization at concentrations >10(-)(5) M. Cyclic voltammetry shows that all three Mn(III) ions were oxidized simultaneously to Mn(IV) at potentials close to 300 mV at pH 12. Electroreduction to Mn(II) was often not observed in the trimers, although the monomers reacted readily under the same conditions. Quantitative chemical reduction of Mn(III) to Mn(II) porphyrin trimers was, however, achieved with dithionite. Trimers containing three paramagnetic Mn(II) or Mn(IV) ions are thus easily accessible. The heterodimers and -trimers and homodimers also catalyzed the formation of dioxygen by electrooxidation of Mn(III) to Mn(IV) between 0.6 and 2.0 V while at pH 12.