A novel system of self-reproducing giant vesicles

Novel self-reproducing giant vesicles, consisting of a vesicular amphiphile with an imine group in its hydrophobic chain, were constructed. This vesicular amphiphile, the product of a dehydrocondensation reaction between amphiphilic aldehyde and a lipophilic aniline derivative, could be prepared within the giant vesicles. When a protected form of the aldehyde precursor was added to a suspension of giant vesicles containing the lipophilic aniline precursor and a catalyst, dehydrocondensation between the two precursors took place inside the vesicles and produced the same amphiphile as the one which constitutes the original vesicle. The newly formed amphiphiles self-assembled in the inner water pool to form small vesicles, which were eventually extruded through the outer layer of the original vesicle to the bulk water. Accordingly, this kinetic system can be designated as a self-reproducing system of giant vesicles.     

Stabilized vesicles consisting of small amphiphiles for stepwise photorelease via UV light

A small amphiphile consisting of hydrophilic tetraethylene glycol monoacrylate and hydrophobic alkyl chain which were connected by an o-nitrobenzyl unit, a photolabile group, was designed and synthesized. The critical aggregate concentration of the synthesized amphiphile was determined to be about 3 × 10(-5) M by the fluorescence probe technique. Nanosized vesicles were prepared and stabilized by in-situ radical polymerization without altering the morphology. The polymeric vesicle was highly stable which retained vesicular shape under dilution or UV irradiation. Hydrophobic guests can be encapsulated within the vesicle membrane and released out of the vesicle by UV stimulus through splitting the amphiphilic structure of the amphiphile. Distinguished dose-controlled photorelease of the polymeric vesicle is achieved due to the maintenance of the vesicular shape integrity which makes the guest release depend on the cleavage amount of amphiphilic structure during UV irradiation. This study provides a promising strategy to develop stable drug delivery systems for sustained and phototriggered release.     

A Versatile and Robust Vesicle Based on a Photocleavable Surfactant for Two‐Photon‐Tuned Release

A small amphiphile that contains a coumarin unit and alkynyl groups, as a two‐photon‐cleavable segment and polymerizable groups, respectively, was designed and synthesized. The amphiphile showed a critical aggregation concentration of about 4.6×10^?5 M and formed a vesicle‐type assembly. The formed vesicles were stabilized by in situ “click” polymerization without altering their morphology. Hydrophobic and hydrophilic guests can be encapsulated within the vesicle membrane and inside the aqueous core of the vesicle, respectively. The loaded guests can be released from the vesicle by using UV or near‐IR stimuli, through splitting up the amphiphilic structure of the amphiphile. Distinguished dose‐controlled photorelease of the polymeric vesicle is achieved with the maintenance of vesicular integrity, which makes the guest release dependent on the amount of cleavage of the amphiphilic structure during irradiation. This study provides a potential strategy for the development of versatile and stable drug‐delivery systems that offer sustained and photo‐triggered release.     

Self-assembled vesicles from amphiphilic platinum(II) terpyridyl complex in water

A new cationic amphiphile (1) functionalised with platinum(II) terpyridyl unit was designed and synthesised to realize self-assembly in water. Using UV–vis and emission spectroscopy, scanning electron microscopy, cryogenic transmission electron microscopy, dynamic light scattering and time-correlated single-photon counting technique, we have demonstrated that amphiphile 1 can self-assemble into stable vesicular aggregates upon direct dissolution in water, which is rarely observed in the literature.     

Macromolecule-to-Amphiphile Conversion Process of a Polyoxometalate-Polymer Hybrid and Assembled Hybrid Vesicles

We report our findings on the macromolecule-to-amphiphile conversion process of a polyoxometalate-polymer hybrid and the assembled hybrid vesicles formed by aggregation of the hybrid amphiphile. The polyoxometalate-polymer hybrid is composed of a polyoxometalate (POM) cluster, which is covered by five tetrabutylammonium (Bu(4) N(+) ) countercations, and a polystyrene (PS) chain. Through a cation-exchange process the Bu(4) N(+) countercations can be replaced by protons to form a hybrid amphiphile composed of a hydrophilic, protonated POM cluster and a hydrophobic PS chain. By implementing a directed one-dimensional diffusion and analyzing the diffusion data, we confirmed that the diffusion of solvated protons rather than macromolecules or aggregates is the key factor controlling the conversion process. Once the giant hybrid amphiphiles were formed, they immediately assembled into kinetically favored vesicular aggregates. During subsequent annealing these vesicular aggregates were transformed into thermodynamically stable vesicular aggregates with a perfect vesicle structure. The success in the preparation of the POM-containing hybrid vesicles provides us with an opportunity of preparing POM-functionalized vesicles.     

新型含苯硼酸和萘双亲化合物的合成与囊泡荧光传感器的制备

合成了含有识别基团苯硼酸和荧光基团萘的新型对-[(5-十二烷氧基-1-氧基)萘]甲基苯硼酸{p-[(5-dodecyloxy-1-oxy) naphthalene] methyl-phenylboronic acid, DNMPBA}双亲化合物; 该化合物在THF/水选择性溶剂中自组织成囊泡, 囊泡的相变温度为56.8 ℃; 当向囊泡体系加糖时, DNMPBA囊泡中的萘生色基在345 nm的荧光峰强度急剧增强; 荧光强度随添加不同糖的变化趋势为果糖>葡萄糖>麦芽糖>乙二醇. 荧光强度增强可能归因于所形成的硼酸酯减弱了DNMPBA双亲化合物中一个氧原子孤对电子对萘生色基的猝灭作用而使荧光强度重新恢复. DNMPBA囊泡与糖的相互作用导致体系荧光强度变化, 使该体系有可能应用于检测生物物质如糖的化学传感器.     

毛细管区带电泳法研究肾上腺素类药物的手性分离

使用β－环糊精（β－ＣＤ）及β－ＣＤ－羧甲基（ＣＭ－β－ＣＤ）作为手性选择剂,采用毛细管区带电泳法（ＣＺＥ）对去甲肾上腺素、肾上腺素和异丙肾上腺素的手性分离进行了研究。对影响这类药物手性分离的主要因素〔手性选择剂、背景电解质（ＢＧＥ）、分离体系的酸度和温度〕进行了讨论,并对手性识别机理进行了探讨。     

新型含苯硼酸和喹啉的囊泡荧光多糖传感器的制备

利用合成的含有识别基团苯硼酸和荧光读出基团喹啉的新型双亲化合物对硼酸苯甲基-8-十六烷氧基溴化喹啉(BHQB)在水中自组织成囊泡,囊泡的相变温度为52.4℃;当向囊泡体系加糖时,BHQB囊泡中的喹啉生色基在508nm的荧光峰强度急剧减弱,425nm处荧光逐渐增强.荧光强度变化可能归于所形成的硼酸酯改变了双亲化合物中硼原子的杂化轨道形式,进一步引起了整个分子内部的电子云排布所致.BHQB囊泡与糖的相互作用而导致体系荧光强度变化,并且这种变化的幅度与加入糖的种类和量均有关.因此体系有可能应用于检测生物物质如糖的化学传感器.     

检测维生素C的囊泡荧光传感器的制备

利用合成的含有识别基团苯硼酸和荧光读出基团萘的新型双亲化合物(DNMPBA)在THF/水选择性溶剂中自组织成囊泡,囊泡的相变温度为56.8℃;当向囊泡体系加维生素C时,DNMPBA囊泡中的萘生色基在345nm的荧光峰强度急剧减弱.荧光强度减弱归于所形成的硼酸酯增强了DNMPBA双亲化合物中一个氧原子孤对电子对萘生色基的淬灭作用.DNMPBA囊泡与维生素C的相互作用而导致体系荧光强度变化,使该体系有可能应用于检测生物物质如维生素C的化学传感器.     

Reduction-responsive vesicles composed of dimethylaminopropyl octadecanamide and dithiodipropionic acid

Reduction-responsive vesicle was prepared by salt-bridging N-[3-(dimethylamino)propyl]-octadecanamide (DMAPODA, a cationic amphiphile) using 3,3′-dithiodipropionic acid (DTPA, a disulfide diacid compound). According to the transmission electron micrograph and the fluorescence quenching degree (53.2%), it could be said that vesicles were formed when the DMAPODA to DTPA molar ratio was 2:2. The DMAPODA/DTPA associate was considered to be a building block for vesicle formation because DTPA could electrostatically associate with DMAPODA and help the cationic amphiphile assemble into the vesicle. On a differential scanning calorimetric thermogram, the DMAPODA/DTPA vesicle showed two endothermic peaks at 50.6°C and 63.2°C. The peak found at the lower temperature was possibly due to the solid gel-to-liquid crystal phase transition of the vesicular membrane and the peak found at the higher temperature was considered to be due to the melting of DMAPODA, indicating that unassociated DMAPODA coexisted with DMAPODA/DTPA vesicles. The release of calcein enveloped in the vesicle was promoted by DL-dithiothreitol, possibly because DTPA can be broken by the reducing agent to form mercaptopropionic acids and the vesicle could be disintegrated and/or the vesicular membrane would become defective.     

Macromolecule-to-Amphiphile Conversion Process of a Polyoxometalate–Polymer Hybrid and Assembled Hybrid Vesicles

We report our findings on the macromolecule-to-amphiphile conversion process of a polyoxometalate–polymer hybrid and the assembled hybrid vesicles formed by aggregation of the hybrid amphiphile. The polyoxometalate–polymer hybrid is composed of a polyoxometalate (POM) cluster, which is covered by five tetrabutylammonium (Bu₄N⁺) countercations, and a polystyrene (PS) chain. Through a cation-exchange process the Bu₄N⁺ countercations can be replaced by protons to form a hybrid amphiphile composed of a hydrophilic, protonated POM cluster and a hydrophobic PS chain. By implementing a directed one-dimensional diffusion and analyzing the diffusion data, we confirmed that the diffusion of solvated protons rather than macromolecules or aggregates is the key factor controlling the conversion process. Once the giant hybrid amphiphiles were formed, they immediately assembled into kinetically favored vesicular aggregates. During subsequent annealing these vesicular aggregates were transformed into thermodynamically stable vesicular aggregates with a perfect vesicle structure. The success in the preparation of the POM-containing hybrid vesicles provides us with an opportunity of preparing POM-functionalized vesicles.     

Bilayer vesicles as precursors for spherical fractal aggregates from the self-assembly of a C60-fullerene-dyad in polar solvent

Spherical fractal aggregates of approximately 10 microm were formed from a pi-electronic amphiphile, C(60)-didodecyloxybenzene dyad when extracted from THF into water, necessitating a critical dielectric constant epsilon > or =30 in binary THF-water mixtures. Molecular dynamics simulations revealed the unit cluster to such a form involves an aggregation number approximately 90 with predominant soft associative molecular interactions which corroborated the octadecahedral model proposed for the cluster growth.     

Functionalization of methyl orange using cationic peptide amphiphile: colorimetric discrimination between ATP and ADP at pH 2.0

A solvatochromic and non-fluorescent acid-base indicator, methyl orange (MO) was applied to colorimetric discrimination between adenosine triphosphate (ATP) and the corresponding diphosphate (ADP) at pH 2.0 in the presence of L-glutamic acid-derived cationic peptide amphiphile 1. This method is based on the fact that the amphiphile 1 can prevent MO from protonation even at pH 2.0. No similar colour change was observed when ADP was added instead of ATP under the same conditions. The effect of the molecular structure of several peptide amphiphiles and dyes was also investigated.     

Beta-cyclodextrin-appended giant amphiphile: aggregation to vesicle polymersomes and immobilisation of enzymes

A giant amphiphile consisting of polystyrene end-capped with permethylated beta-cyclodextrin was synthesised and found to form vesicular structures when injected as a solution in THF into water. The ability of the cyclodextrins on the surface of the polymersomes to form inclusion complexes with hydrophobic compounds was tested by carrying out a competition experiment with a fluorescent probe sensitive to the polarity of the surrounding medium. It was found that 1-adamantol can displace the fluorescent probe from the cavities of the cyclodextrin moieties of the polymersomes. The recognition of molecules by cell membranes in nature is often based on interactions with specific membrane receptors. To mimic this behaviour, the enzyme horseradish peroxidase was modified with adamantane groups through a poly(ethylene glycol) spacer and its interaction with the polymersomes was investigated. It was established that the presence of adamantane moieties on each enzyme allowed a host-guest interaction with the multifunctional surface of the polymersomes.     

Enhancing physical stability of positively charged catanionic vesicles in the presence of calcium chloride via cholesterol-induced fluidic bilayer characteristic

An ion pair amphiphile (IPA), hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS), and a double-chained cationic surfactant, dimethyldimyristylammonium bromide (DTDAB), could form positively charged catanionic vesicles with a potential application in gene delivery. To improve the gene delivery efficiency, the addition of CaCl₂ into cationic liposomal systems has been proposed in the literature. In this study, detrimental effect of calcium chloride on the physical stability of the positively charged HTMA-DS/DTDAB catanionic vesicles was demonstrated by the size and zeta potential analyses of the vesicles. It was noted that the reduced electrostatic interaction between the catanionic vesicles could not fully explain the lowered physical stability of the vesicles in the presence of CaCl₂. Apparently, the molecular packing/interaction in the vesicular bilayers played an important role in the vesicle physical stability. To modify the molecular packing/interaction in the vesicular bilayers, cholesterol was adopted as an additive to form catanionic vesicles with HTMA-DS/DTDAB. It was found that the physical stability of the catanionic vesicles was significantly improved with the presence of cholesterol in the vesicular bilayers even in the presence of 50 mM CaCl₂. An infrared analysis suggested that with the incorporation of cholesterol into HTMA-DS/DTDAB vesicular bilayers, the alkyl chain motion was enhanced, and the molecular packing became less ordered. The cholesterol-induced fluidic bilayer characteristic allowed the vesicular bilayers to be adjusted to a stable status, resulting in improved physical stability of the catanionic vesicles even in the presence of CaCl₂ with a high concentration.     

Swelling of Water/Nonionic Surfactant Lamellar Liquid Crystals: A Model

A model is presented to provide quantitative measures to estimate the trends of the change in the penetration of the added component into the polar part of the amphiphile layer in lamellar liquid crystals of water and ethoxylated surfactants with added water (or polar solvents). The total thickness of the bi‐layer is treated as composed of an aqueous layer, of a layer of the polar groups from the surfactant and of the hydrocarbon chains of the latter. A fraction α of the added water is assumed penetrating the polar group layer leading to its expansion. The evaluation is built on the fact that experimental determinations of the interlayer spacing in the overwhelming majority of cases show a first order linear dependence on the ratio of added water. In the model this linearity is obtained by variation of the degree of penetration of water. The model indicated a reduction in the degree of penetration with added water, which is a rational trend. The model demonstrates the earlier interpretation of a structure, whose interlayer spacing is invariant with water contents as nonswelling; for example, in which all added water penetrates the amhiphile layer, is not appropriate. The model demonstrates the constancy of the interlayer spacing to be a consequence of a balance between the expansion of the amphiphile layer and the increase of a “free water” layer.     

Interactions between Catalysts and Amphiphilic Structures and their Implications for a Protocell Model

One of the essential elements of any cell, including primitive ancestors, is a structural component that protects and confines the metabolism and genes while allowing access to essential nutrients. For the targeted protocell model, bilayers of decanoic acid, a single‐chain fatty acid amphiphile, are used as the container. These bilayers interact with a ruthenium–nucleobase complex, the metabolic complex, to convert amphiphile precursors into more amphiphiles. These interactions are dependent on non‐covalent bonding. The initial rate of conversion of an oily precursor molecule into fatty acid was examined as a function of these interactions. It is shown that the precursor molecule associates strongly with decanoic acid structures. This results in a high dependence of conversion rates on the interaction of the catalyst with the self‐assembled structures. The observed rate logically increases when a tight interaction between catalyst complex and container exists. A strong association between the metabolic complex and the container was achieved by bonding a sufficiently long hydrocarbon tail to the complex. Surprisingly, the rate enhancement was nearly as strong when the ruthenium and nucleobase elements of the complex were each given their own hydrocarbon tail and existed as separate molecules, as when the two elements were covalently bonded to each other and the resulting molecule was given a hydrocarbon tail. These results provide insights into the possibilities and constraints of such a reaction system in relation to building the ultimate protocell.     

Oriented molecular aggregates of porphyrin-based amphiphiles and their morphology control by a boronic acid sugar interaction

Towards the morphology control of oriented porphyrin aggregates by added saccharides, three amphiphilic porphyrins bearing boronic acid groups were synthesised. Among them, an amphiphilic tetraphenylporphyrin (4) bearing two octadecyl groups at 5,10-positions and two boronic acid groups (acting as saccharide-binding sites) at 15,20-positions has been found to act as a membrane-forming amphiphile in an aqueous system. Spectroscopic (UV–Vis and CD), light-scattering, DSC and electron micrographic studies have established that in aqueous media 4 forms stable fibrous aggregates only in the presence of saccharides, which are chirally twisted by the absolute configuration of the added saccharides. This is a novel method to control the aggregate morphology by saccharides and well imitates the morphological functions of certain cell membranes, the surfaces of which are covered by saccharides.     

Synthetic membranes (vesicles) in inorganic ion analysis: a review

Vesicles are structures of amphiphile molecules occurring through a self-aggregation process at the molecular or nano scale level with a large structural variety and diverse properties providing a reaction environment for chemical reactions that resembles that of natural systems. Their high versatility and recognized utility in various applications have triggered a interdisciplinary scientific endeavor over their formation, characterization and potential applications with impressive results. However, in the vastness of applications surrounding vesicular structures, their utility in analytical chemistry has only received minor attention. Notwithstanding, studies demonstrating their potential as colorimetric or fluorescence sensors, extraction solvents of inorganic ions or their chelates and stationary phase modifiers in liquid chromatography have appeared. To this end, this article aims to present for the first time the analytical chemistry aspects behind the use of vesicle media with special emphasis on the detection and determination of inorganic ions and encourage further research on this promising field of analytical science.