Hexayne Amphiphiles and Bolaamphiphiles

Oligoynes with two or more conjugated carbon–carbon triple bonds are useful precursors for carbon-rich nanomaterials. However, their range of applications has so far been severely limited by the challenging syntheses, particularly in the case of oligoynes with functional groups. Here, we report a universal synthetic approach towards both symmetric and unsymmetric, functionalized hexaynes through the use of a modified Eglinton–Galbraith coupling and a sacrificial building block. We demonstrate the versatility of this approach by preparing hexaynes functionalized with phosphonic acid, carboxylic acid, ammonium, or thiol head groups, which serve as neutral, cationogenic, or anionogenic interfacially active groups. We show that these hexaynes are carbon-rich amphiphiles or bolaamphiphiles that self-assemble at liquid–liquid interfaces, on solid surfaces, as well as in aqueous media.     

Preparation and properties of rotaxanes formed by dimethyl-beta-cyclodextrin and oligo(thiophene)s with beta-cyclodextrin stoppers

Novel cyclodextrin rotaxanes with oligothiophene as an axis molecule have been prepared by the Suzuki coupling reaction of 6-O-(4-iodophenyl)-beta-CD (6-I-Ph-beta-CD) with di(1,3,2-dioxaborolan-2-yl)-oligothiophene (oligothiophene diboric ethylene glycol esters) in aqueous solutions of dimethyl-beta-cyclodextrin (DM-beta-CD). These reactions gave [2]rotaxanes and [3]rotaxanes, which were isolated by reversed phase chromatography. The fluorescence intensities of rotaxanes are higher than those of dumbbell-shaped molecules (without DM-beta-CD) in aqueous solutions. The inclusion ratio and chain length of rotaxanes have been found to relate to the emission properties and emission intensities of oligothiophene. In aqueous solutions, fluorescence quantum yields of rotaxanes are higher than those of dumbbell-shaped molecules. The increase in the fluorescence efficiency of rotaxane is caused by suppression of intermolecular interactions, indicating the effect of insulated oligothiophene with DM-beta-CD. beta-CD at the both ends of rotaxanes functions not only as bulky stoppers but also as the recognition site for guest molecules, as verified by fluorescence quenching experiments.     

Electrochemical properties of 3,5-diphenylaniline units encapsulated within a crown ether. Effects of the macrocycle’s aromatic functionality and ring size

This Letter describes a series of [2]rotaxanes featuring a 3,5-diphenylaniline terminus in their dumbbell-shaped component and crown ethers as the macrocyclic component, prepared through imine formation and hydrogen bond—guided self-assembly. Electrochemical studies of these [2]rotaxanes revealed that the oxidation potential of the aniline moiety when positioned within the cavity of a crown ether was shifted negatively relative to that of the corresponding dumbbell-shaped compound, and that a crown ether possessing a small cavity and a large number of aromatic rings had a more negative effect on the oxidation potential of the aniline moiety than did a large-cavity crown ether featuring no aromatic rings. UV experiments showed that absorption band of the rotaxanes bearing small crowns shifted to longer wavelengths as compared to those of the rotaxanes having large crowns.     

Polyglycerol-derived amphiphiles for the solubilization of single-walled carbon nanotubes in water: a structure-property study

A series of nonionic amphiphiles derived from polyglycerol dendrons were studied for their ability to solubilize and isolate single-walled carbon nanotubes. The amphiphiles possessed differently sized polar head groups, hydrophobic tail units, and various aromatic and non-aromatic groups between the head and tail groups. Absorbance analysis revealed that amphiphiles with anchor groups derived from pyrene were far inferior to those that possessed simple linear aliphatic tail groups. Absorbance and near-infrared fluorescence analyses revealed a weak dependence on the dendron size of the head group, but a strong positive trend in suspended nanotube density and fluorescence intensity for amphiphiles with longer tail units. Variations in the moieties linking the head and tail groups led to a range of effects on the suspensions, with linkers imparting flexibility and a bent shape that gave improved performance overall. This was illustrated most dramatically by a pair of benzamide-containing amphiphiles, the para isomer of which showed evidence in the fluorescence data of increased nanotube aggregate formation when compared with the meta isomer. In addition, statistical AFM was used to illustrate more directly the microscopic differences between amphiphiles that were effective at nanotube bundle disruption and those that were not.     

Dynamic octopus amphiphiles as powerful activators of DNA transporters: differential fragrance sensing and beyond

We report the design, synthesis and evaluation of dynamic "octopus" amphiphiles with emphasis on their efficiency as activators in synthetic membrane-based sensing systems. Previously, we found that the in situ treatment of charged hydrazides with hydrophobic aldehydes or ketones gives amphiphilic counterion activators of polyion transporters in lipid bilayers, and that their efficiency increases with the number of their hydrophobic tails. Herein, we expand this series to amphiphiles with one cationic head (guanidinium or ammonium) and four exchangeable hydrophobic tails. These results, with the highest number of tails reported to date, confirm that dynamic octopus amphiphiles provide access to maximal activity and selectivity. Odorants, such as muscone, carvone, or anisaldehyde are used to outline their usefulness in differential sensing systems that operate based on counterion-activated DNA transporters in fluorogenic vesicles. The enhanced ability of octopus amphiphiles to enable the discrimination of enantiomers as well as that of otherwise intractable ortho, meta, and para isomers and short cyclo-/alkyl tails is demonstrated. These findings identify dynamic octopus amphiphiles as being promising for application to differential sensing, "fragrant" cellular uptake, and slow release.     

环糊精相关的超分子自组装最新进展

对基于环糊精的超分子自组装的最新研究进展作了综述.详细介绍了环糊精为轮、高分子为轴的聚轮烷的制备及其修饰的方法,同时还介绍了无高分子参与的环糊精的超分子自组装高分子化合物的制备.并且对这些超分子在智能材料、生物医药和聚合催化等方面的应用进行了介绍.     

Synthesis and properties of conjugated oligoyne-centered π-extended tetrathiafulvalene analogues and related macromolecular systems

Alkynyl-substituted phenyldithiafulvenes have been found to act as versatile building blocks for the construction of π-conjugated molecular rods, shape-persistent macrocycles (SPMs), and conducting polymers. Through Cu(I)-catalyzed alkynyl homocoupling, a series of linear-shaped π-extended tetrathiafulvalene analogues (exTTFs) carrying conjugated oligoynes (ranging from diyne to hexayne) as the central π-bridge were readily prepared. The solid-state properties and reactivities of diyne- and tetrayne-centered exTTFs were characterized by X-ray crystallography and differential scanning calorimetry (DSC), while the electronic properties of the oligoyne-exTTFs were elucidated by UV-vis absorption spectroscopy and density functional theory (DFT) calculations. Cyclic voltammetric analysis showed that the terminal phenyldithiafulvene groups of the oligyne-exTTFs could undergo oxidative coupling to form tetrathiafulvalene vinylogue (TTFV)-linked polymer wires. Through a different synthetic route involving oxidative dimerization and Pd/Cu-catalyzed alkynyl homocoupling, the acetylenic phenyldithiafulvene precursors led to shape-persistent macrocycles where the formation of trimeric macrocycles was particularly favored due to the small ring strain incurred. Finally, spectroelectrochemical studies on these oligoyne and TTF hybrid materials disclosed electrochromic and molecular redox-controlled switching properties applicable to molecular electronic and optoelectronic devices.     

The structure of interlocked helical supramolecule formed by the self-assembly of mono-6-(4-cyano-phenyl)-β-cyclodextrin

The supramolecular self-assembly formed by newly synthesized mono-6-(4-cyano-phenyl)-β-cyclodextrin through the molecular interpenetration has been investigated and compared in both solution and the solid state, which was characterized by X-ray crystallography, fourier transform infrared spectroscopy, NMR spectroscopy and atomic force microscopy. The crystal structure clearly revealed that the benzonitrile group is consecutively inserted into the adjacent cyclodextrin cavity from the second side, thus giving rise to an unusual interlocked helical supramolecular self-assembly in which the benzonitrile group acts as bridge between the cyclodextrin units. As compared with crystal, the conformation in aqueous solution indicates that the benzonitrile group prefer to be self-assembled included into another cavity from the second side of cyclodextrin to form the self-assembly.     

Aggregation behavior of giant amphiphiles prepared by cofactor reconstitution

We report on biohybrid surfactants, termed "giant amphiphiles", in which a protein or an enzyme acts as the polar head group and a synthetic polymer as the apolar tail. It is demonstrated that the modification of horseradish peroxidase (HRP) and myoglobin (Mb) with an apolar polymer chain through the cofactor reconstitution method yields giant amphiphiles that form spherical aggregates (vesicles) in aqueous solution. Both HRP and Mb retain their original functionality when modified with a single polystyrene chain, but reconstitution has an effect on their activities. In the case of HRP the enzymatic activity decreases and for Mb the stability of the dioxygen myoglobin (oxy-Mb) complex is reduced, which is probably the result of a disturbed binding of the heme in the apo-protein or a reduced access of the substrate to the active site of the enzyme or protein.     

Self-assembly and supramolecular transition of poly(amidoamine) dendrons focally modified with aromatic chromophores

Three novel series of amphiphiles based on poly(amidoamine) dendrons (from G1 to G3) and having different aromatic chromophores (Cz I, Cz II, and Py) at the focal point were synthesized and studied for their self-assembly behavior in aqueous solution by using electronic microscopies (i.e., SEM and TEM), UV-vis, fluorescence, IR, and (1)H NMR spectroscopy. It was found that the generation of dendrons affected significantly the self-assembly of these amphiphiles in aqueous solution and the morphological structures of the resulting assemblies depended greatly on the architecture of the focal chromophores. As a result, the first generation of dendrons assembled readily into vesicles at low concentrations. These vesicular structures subsequently fused to form a stable tubular structure. Similar tubular structures could also be directly obtained through self-assembly of these amphiphilic dendrons at high concentrations. X-ray investigations showed that the resulting tubules possessed a lamellar structure. A head-to-head packing model of amphiphilic dendrons in the assemblies was proposed.     

Carbodiimide-Driven Dimerization and Self-Assembly of Artificial,Ribose-Based Amphiphiles

The aqueous self-assembly of amphiphiles into aggregates such as micelles and vesicles has been widely investigated over the past decades with applications ranging from materials science to drug delivery. The combination of characteristic properties of nucleic acids and amphiphiles is of substantial interest to mimic biological self-organization and compartmentalization. Herein, we present ribose- and ribonucleotide-based amphiphiles and investigate their self-assembly as well as their fundamental reactivity. We found that various types of aggregates are formed, ranging in size from nanometers to micrometers and all amphiphiles exhibit aggregation-induced emission (AIE) in solution as well as in the solid state. We also observed that the addition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) leads to rapid and selective dimerization of the amphiphiles into pyrophosphates, which decreases the critical aggregation concentration (CAC) by a factor of 25 when compared to the monomers. Since the propensity for amphiphile dimerization is correlated with their tendency to self-assemble, our results may be relevant for the formation of rudimentary compartments under prebiotic conditions.     

Biologically Active Heteroglycoclusters Constructed on a Pillar[5]arene‐Containing [2]Rotaxane Scaffold

A synthetic approach combining recent concepts for the preparation of multifunctional nanomolecules (click chemistry on multifunctional scaffolds) with supramolecular chemistry (self‐assembly to prepare rotaxanes) gave easy access to a large variety of sophisticated [2]rotaxane heteroglycoclusters. Specifically, compounds combining galactose and fucose have been prepared to target the two bacterial lectins (LecA and LecB) from the opportunistic pathogen Pseudomonas aeruginosa.     

Rapid access to phospholipid analogs using thiol-yne chemistry

Phospholipids and glycolipids constitute an essential part of biological membranes, and are of tremendous fundamental and practical interest. Unfortunately, the preparation of functional phospholipids, or synthetic analogs, is often synthetically challenging. Here we utilize thiol-yne click chemistry methodology to gain access to phospho- and glycolipid analogs. Alkynyl hydrophilic head groups readily photoreact with numerous thiol modified lipid tails to yield the appropriate dithioether phospho- or glycolipids. The resulting structures closely resemble the structure and function of native diacylglycerolipids. Dithioether phosphatidylcholines (PCs) are suitable for forming giant unilamellar vesicles (GUV), which can be used as vessels for cell-free expression systems. The unnatural thioether linkages render the lipids resistant to phospholipase A2 hydrolysis. We utilize the improved stability of these lipids to control the shrinkage of GUVs composed of a mixture of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and dioleyl-dithioether PC, concentrating encapsulated nanoparticles. We imagine that these readily accessible lipids could find a number of applications as natural lipid substitutes.     

Supramolecular Hybrids from Cyanometallate Complexes and Diblock Copolypeptide Amphiphiles in Water

The self-assembly of discrete cyanometallates has attracted significant interest due to the potential of these materials to undergo soft metallophilic interactions as well as their optical properties. Diblock copolypeptide amphiphiles have also been investigated concerning their capacity for self-assembly into morphologies such as nanostructures. The present work combined these two concepts by examining supramolecular hybrids comprising cyanometallates with diblock copolypeptide amphiphiles in aqueous solutions. Discrete cyanometallates such as [Au(CN)₂]⁻, [Ag(CN)₂]⁻, and [Pt(CN)₄]²⁻ dispersed at the molecular level in water cannot interact with each other at low concentrations. However, the results of this work demonstrate that the addition of diblock copolypeptide amphiphiles such as poly-(L-lysine)-block-(L-cysteine) (Lys_m-b-Cys_n) to solutions of these complexes induces the supramolecular assembly of the discrete cyanometallates, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Electron microscopy images confirmed the formation of nanostructures of several hundred nanometers in size that grew to form advanced nanoarchitectures, including those resembling the original nanostructures. This concept of combining diblock copolypeptide amphiphiles with discrete cyanometallates allows the design of flexible and functional supramolecular hybrid systems in water.     

Asymmetric Resolution in Ester Reduction by NaBH4 at the Interface of Aqueous Aggregates of Amino Acid,Peptide, and Chiral‐Counterion‐Based Cationic Surfactants

This study provides insight into the physicochemical aspects of aqueous aggregates that comprise amino acid, peptide, and chiral‐counterion‐based cationic surfactants and their correlation with the proficiency of asymmetric resolution in ester reduction. The effects of the structural differences in the naturally occurring amino acid based and synthetic chiral‐counterion‐containing gemini surfactants on the surface properties as well as on other microstructural parameters were studied and correlated to the varied head groups of the surfactants. The supramolecular chirality induced from the head‐group region of chiral amphiphiles in aqueous self‐aggregates is evident from circular dichroism, scanning electron microscopy, and transmission electron microscopy studies. This large‐scale chirality at the interface of self‐aggregates was exploited towards asymmetric resolution in ester reduction by NaBH₄. An enantiomeric excess of 53 % ((R)‐2‐phenylpropan‐1‐ol) was found in the case of the n‐hexyl ester of 2‐phenylpropionic acid as substrate in the aqueous aggregate of N,N′‐dihexadecyl‐N,N,N′,N′‐tetramethyl‐N,N′‐ethanediyldiammonium diquinate. Thus, a simple and environmentally benign pathway for asymmetric resolution in ester reduction by sodium borohydride alone is reported, which utilizes the varied spatial asymmetry at the interface of aqueous aggregates of cationic chiral amphiphiles.     

Synthesis and characterization of heptaphenyl polyhedral oligomeric silsesquioxane-capped poly(N-isopropylacrylamide)s

In this work, a novel initiator bearing heptaphenyl polyhedral oligomeric silsesquioxane (POSS) was synthesized via the copper-catalyzed Huisgen 1,3-cycloaddition (i.e., click chemistry). With this initiator, the atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAAm) was carried out to afford the POSS-capped PNIPAAm. The organic–inorganic amphiphiles were characterized by means of nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). Atomic force microscopy (AFM) showed that the POSS-capped PNIPAAm amphiphiles in bulk displayed microphase-separated morphologies. In aqueous solutions, the POSS-capped PNIPAAm amphiphiles were self-assembled into micelle-like aggregates as evidenced by dynamic light scattering (DLS) and transmission election microscopy (TEM). It was found that the sizes of the self-organized nanoobjects decreased with increasing the lengths of PNIPAAm chains. By means of UV–vis spectroscopy, the lower critical solution temperature (LCST) behavior of the organic–inorganic amphiphiles in aqueous solution was investigated and the LCSTs of the organic–inorganic amphiphiles decreased with increasing the percentage of POSS termini. It is noted that the self-assembly behavior of the POSS-capped PNIPAAm in aqueous solutions exerted the significant restriction on the macromolecular conformation alteration of PNIPAAm chains while the coil-to-globule collapse occurred.     

A structural remedy toward bright dipolar fluorophores in aqueous media

The donor–acceptor (D–A) type dipolar fluorophores, an important class of luminescent dyes with two-photon absorption behaviour, generally emit strongly in organic solvents but poorly in aqueous media. To understand and enhance the poor emission behaviour of dipolar dyes in aqueous media, we undertake a rational approach that includes a systematic structure variation of the donor, amino substituent of acedan, an important two-photon dye. We identify several factors that influence the emission behaviour of the dipolar dyes in aqueous media through computational and photophysical studies on new acedan derivatives. As a result, we can make acedan dyes emit bright fluorescence under one- and two-photon excitation in aqueous media by suppressing the liable factors for poor emission: 1,3-allylic strain, rotational freedom, and hydrogen bonding with water. We also validate that these findings can be generally extended to other dipolar fluorophores, as demonstrated for naphthalimide, coumarin and (4-nitro-2,1,3-benzoxadiazol-7-yl)amine (NBD) dyes. The new acedan and naphthalimide dyes thus allow us to obtain much brighter two-photon fluorescent images in cells and tissues than in their conventional forms. As an application of these findings, a thiol probe is synthesized based on a new naphthalimide dye, which shows greatly enhanced fluorescence from the widely used N,N-dimethyl analogue. The results disclosed here provide essential guidelines for the development of efficient dipolar dyes and fluorescence probes for studying biological systems, particularly by two-photon microscopy.     

Self-assembly of cyclic hexamers of γ-cyclodextrin in a metallosupramolecular framework with d-penicillamine

Cyclodextrins are widely used cyclic oligosaccharides of d-glucose whose hydrophilic exterior is covered by hydroxyl groups and whose hydrophobic interior is surrounded by lipophilic moieties. Because of this structural feature, cyclodextrin molecules commonly aggregate into dimensional structures via intermolecular hydrogen bonds, and their aggregation into closed oligomeric architectures has been achieved only via the attachment of functional substituent groups to the cyclodextrin rings. Here, we report the first structurally characterized self-assembly of non-substituted γ-cyclodextrin molecules into cyclic hexamers, which was realized in a chiral coordination framework composed of complex-anions with d-penicillamine rather than l- or dl-penicillamine. The self-assembly is accompanied by the 3D-to-2D structural transformation of porous coordination frameworks to form helical hexagonal cavities that accommodate helical γ-cyclodextrin hexamers. This finding provides new insight into the development of cyclodextrin chemistry and host–guest chemistry based on chiral recognition and crystal engineering processes.

The complex anions with d-penicillamine are organized into a 3D porous framework that allows the inclusion of γ-CD. The inclusion is accompanied by the 3D-to-2D transformation of porous frameworks so as to accept cyclic hexamers of γ-CD.     

Cyclodextrin‐Based Size‐Complementary [3]Rotaxanes: Selective Synthesis and Specific Dissociation

α‐Cyclodextrin (CD)‐based size‐complementary [3]rotaxanes with alkylene axles were prepared in one‐pot by end‐capping reactions with aryl isocyanates in water. The selective formation of [3]rotaxane with a head‐to‐head regularity was indicated by the X‐ray structural analyses. Thermal degradation of the [3]rotaxanes bearing appropriate end groups proceeded by stepwise dissociation to yield not only the original components but also [2]rotaxanes. From the kinetic profiles of the deslippage, it turned out that the maximum yield of [2]rotaxane was estimated to be 94 %. Thermodynamic studies and NOESY analyses of such rotaxanes revealed that [2]rotaxanes are specially stabilized, and that the dissociation capability of the [3]rotaxanes to the components can be adjusted by controlling the structure of the end groups, direction of the CD groups, and length of the alkylene axle.     

Self-assembly in aqueous bile salt solutions

The salts of bile acids (“bile salts”) self-assemble in aqueous solution, similar to classical amphiphiles. The micellization is not only driven by the hydrophobic effect, but also hydrogen binding. Moreover, instead of a small, hydrophilic head and a flexible, hydrophobic tail, bile salts are rigid, almost flat molecules with weakly separated hydrophobic and hydrophilic faces. This results in a complex self-assembly behaviour with very distinct aggregate properties. Some characteristics resemble the behaviour of classical amphiphiles, while others are very different and reminiscent of other classes of molecules, for example low-molecular weight gelators or chromonic materials. We review the peculiar properties of bile salt aggregates, concentrating on general trends rather than specific values and comparing them to classical amphiphiles.