表面活性离子液体参与构筑的胶束体系

离子液体的可设计性,使得新型表面活性离子液体不断涌现,从而将具有不同功能基团的离子液体引入到了传统的有序分子聚集体中,这也将有助于实现有序分子聚集体的可控性和功能化。本文综合评述了表面活性离子液体在水溶液及离子液体中的胶束化行为,重点总结了烷基碳链长度、阴离子结构和阳离子结构对表面活性离子液体聚集行为的影响,介绍了新型功能性表面活性离子液体在水溶液中的胶束化行为,分析了表面活性离子液体与传统表面活性剂复配体系的协同增效作用,并探讨了表面活性离子液体构建的胶束体系的发展方向。     

Anionic surfactants and surfactant ionic liquids with quaternary ammonium counterions

Small-angle neutron scattering and surface tension have been used to characterize a class of surfactants (SURFs), including surfactant ionic liquids (SAILs). These SURFs and SAILs are based on organic surfactant anions (single-tail dodecyl sulfate, DS, double-chain aerosol-OT, AOT, and the trichain, TC) with substituted quaternary ammonium cations. This class of surfactants can be obtained by straightforward chemistry, being cheaper and more environmentally benign than standard cationic SAILs. A surprising aspect of the results is that, broadly speaking, the physicochemical properties of these SURFs and SAILs are dominated by the nature of the surfactant anion and that the chemical structure of the added cation plays only a secondary role.     

Bola型表面活性剂合成及其应用*

介绍了Bola型表面活性剂独特的结构特征与性质,概述了由Bola型两亲分子在气液界面自组装形成的单分子膜及囊泡的特征。重点综述了Bola型表面活性剂的合研究进展,并对其在纳米材料、药物缓释、生物矿化、光化学修饰及抑止金属腐蚀等方面的应用作了介绍。最后对其研究前景作了展望。     

离子型表面活性剂自组装体系在化学中的应用

本文介绍了离子型表面活性剂在氧化物表面自组装体系的原理及特点，离子型表面活性剂分子从溶液中自发地吸附到氧化物表面形成单分子胶束、双分子胶束和混合胶束，该体系对许多疏水性有机化合物以及经螯合有机基团的金属离子具有很强的吸附富集作用，本文根据不同自组装体系的结构分类详述了它们在分析化学和环境化学中应用研究，并且展望了该技术的应用前景。     

Synthesis of vesicles on polymer template

Reactive single-tail cationic surfactants self-assemble on the anionic block copolymer templates. These systems spontaneously arrange in small vesicles of nanoscale size. The vesicles are further stabilized by dimerization of the assembled surfactant monomers forming double-tail surfactants bound to the block copolymer. The resulting systems are resistant to changes in environmental characteristics such as pH, ionic strength, and temperature variations. Hydrophilic macromolecules can be encapsulated in the internal aqueous volume of these vesicles. The simplicity of the preparation makes these systems promising as drug and gene delivery carriers.     

离子液体表面活性剂1-丁基-3-甲基咪唑烷基硫酸酯的合成及其在水溶液中的聚集行为

采用离子交换法,由1-丁基-3甲基咪唑氯盐（C4mimCl）和烷基硫酸钠合成了一系列无卤素的阴离子表面活性离子液体—1-丁基-3-甲基咪唑烷基硫酸酯[C4mim][CnH2n 1SO4](n=8,12,16),利用表面张力仪、稳态荧光光谱等手段考察了表面活性离子液体在水溶液表面及体相中的聚集行为,结果表明,与传统无机反离子相比,有机咪唑阳离子[C4mim] 作为反离子的离子液体型表面活性剂具有较高的表面活性,[C4mim] 产生的氢键引起的抑制分子规则排列的作用小于其促进分子有序排列的疏水作用。长烷基链的阴离子是界面膜及胶束的主要组成成分,阴离子疏水烷基碳链的增长虽然可促进胶束的形成,但却在一定程度上抑制[C4mim] 离子参与界面或胶束的形成;阴离子所带烷基链越长,越不利于阳离子[C4mim]＋参与界面膜或胶束的形成,界面膜或胶束中表面活性剂排布越松散,即界面张力越大,体系中胶束聚集数较小。     

Biodegradable polymeric nanoparticles based on amphiphilic principle: construction and application in drug delivery

The use of nanotechnology in drug-delivery systems (DDS) is attractive for advanced diagnosis and treatment of cancer diseases. Biodegradable polymeric nanoparticles, for example, have promising applications as advanced drug carriers in cancer treatment. In this review, we discuss the development of drug-delivery systems based on an amphiphilic principle mainly conducted by our group for anti-cancer drug delivery. We first briefly address the synthetic chemistry for amphiphilic biodegradable polymers. In the second part, we summarize progress in the application of self-assembled polymer micelles using amphiphilic biodegradable copolymers as anti-tumor drug carriers.     

DNA纳米结构在药物转运载体和智能载药中的应用进展

纳米材料具有荷载效率高、靶向性能好、半衰期较长等优点, 非常适于作为药物转运载体, 可有效提高药物的水溶性、稳定性和疾病治疗效果.目前, 开发具有良好生物相容性、可控靶向释放能力和精确载药位点的理想药物转运载体, 仍是该领域存在的挑战性问题和当前研究的重点.自组装DNA纳米结构是一类具有精确结构、功能多样的纳米生物材料, 具有良好的生物相容性和稳定性、较高的膜渗透性和可控靶向释放能力等优点, 是理想的药物转运载体和智能载药材料.本文总结了DNA纳米结构的发展历程、DNA纳米结构作为药物转运载体的研究现状、动态DNA纳米结构在智能载药中的应用进展, 并对其发展前景进行了展望.     

Cyclodextrin based novel drug delivery systems

The versatile pharmaceutical material cyclodextrin’s (CDs) are classified into hydrophilic, hydrophobic, and ionic derivatives. By the early 1950s the basic physicochemical characteristics of cyclodextrins had been discovered, since than their use is a practical and economical way to improve the physicochemical and pharmaceutical properties such as solubility, stability, and bioavailability of administered drug molecules. These CDs can serve as multi-functional drug carriers, through the formation of inclusion complex or the form of CD/drug conjugate and, thereby potentially serving as novel drug carriers. This contribution outlines applications and comparative benefits of use of cyclodextrins (CDs) and their derivatives in the design of novel delivery systems like liposomes, microspheres, microcapsules, nanoparticles, cyclodextrin grafted cellulosic fabric, hydrogels, nanosponges, beads, nanogels/nanoassemblies and cyclodextrin-containing polymers. The article also focuses on the ability of CDs to enhance the drug absorption across biological barriers, the ability to control the rate and time profiles of drug release, drug safety, drug stability, and the ability to deliver a drug to targeted site. The article highlight’s on needs, limitations and advantages of CD based delivery systems. CDs, because of their continuing ability to find several novel applications in drug delivery, are expected to solve many problems associated with the delivery of different novel drugs through different delivery routes.     

DNA Nanostructures as Drug Carriers for Cellular Delivery

Drug delivery systems have been widely developed for enhancing target activity and improving drug functions.Liposomes,high-molecular polymer,gold nanoparticles and carbon nanomaterials,etc.,are all the candidates of drug carriers.However,immunotoxicity,heterogeneity and low solubility generally exist and hamper their applications.As a kind of biological materials,DNA has its unique advantages in biomedical applications,including excellent biological compatibility and programmability.DNA nanostructures have been proved to possess high cellular uptake efficiency,which sheds new light on DNA-based drug delivery system.In this review,we summarize the influence factors of DNA nanostructure internalization efficiency,including cell lines,and the size and the shape of DNA nanoparticles.Uniformity of DNA nanostructures in appearance and properties ensures the stability in research,which makes DNA carriers stand out from other nanomaterials.Next,we focus on the functionalization of DNA carriers,which endows DNA nanostructures with the potential to construct integrated drug delivery platforms.We also discuss the internalization pathways of DNA nanostructures and their fate in cells.The deeply understanding about the endocytic pathways provides new sight for the further design strategy on changing the transportation routes of DNA carriers in cells.Finally,the challenges in further applications are discussed,and suggestions are proposed.     

Study of the Cloud Point of the Phenothiazine Drug Chlorpromazine Hydrochloride: Effect of Surfactants and Polymers

Surfactants/polymers are used extensively in drug delivery as drug carriers. We herein report the effect of surfactants and polymers on the cloud point (CP) of amphiphilic drug chlorpromazine hydrochloride. At fixed drug concentration (50 mM) and pH (6.7) these additives affect the CP in accordance to their nature and structure: anionic surfactants show an increase followed by a decrease, whereas cationic (conventional as well as gemini) and nonionic surfactants show continous increase. The behavior with polymers is dictated by the number of units present in a particular polymer. Increase in drug concentration and pH, in presence of fixed amounts of CTAB, increases and decreases the CP, respectively. Variation of CP with pH at various fixed gemini concentrations shows that gemini surfactants are better candidates for drug delivery.     

Self-Assembling Drug Formulations with Tunable Permeability and Biodegradability

This review focuses on key topics in the field of drug delivery related to the design of nanocarriers answering the biomedicine criteria, including biocompatibility, biodegradability, low toxicity, and the ability to overcome biological barriers. For these reasons, much attention is paid to the amphiphile-based carriers composed of natural building blocks, lipids, and their structural analogues and synthetic surfactants that are capable of self-assembly with the formation of a variety of supramolecular aggregates. The latter are dynamic structures that can be used as nanocontainers for hydrophobic drugs to increase their solubility and bioavailability. In this section, biodegradable cationic surfactants bearing cleavable fragments are discussed, with ester- and carbamate-containing analogs, as well as amino acid derivatives received special attention. Drug delivery through the biological barriers is a challenging task, which is highlighted by the example of transdermal method of drug administration. In this paper, nonionic surfactants are primarily discussed, including their application for the fabrication of nanocarriers, their surfactant-skin interactions, the mechanisms of modulating their permeability, and the factors controlling drug encapsulation, release, and targeted delivery. Different types of nanocarriers are covered, including niosomes, transfersomes, invasomes and chitosomes, with their morphological specificity, beneficial characteristics and limitations discussed.     

Surface active ionic liquids: study of the micellar properties of 1-(1-alkyl)-3-methylimidazolium chlorides and comparison with structurally related surfactants

The impetus for the increasing interest in studying surface active ionic liquids (SAILs; ionic liquids with long-chain "tails") is the enormous potential for their applications, e.g., in nanotechnology and biomedicine. The progress in these fields rests on understanding the relationship between surfactant structure and solution properties, hence applications. This need has prompted us to extend our previous study on 1-(1-hexadecyl)-3-methylimidazolium chloride to 1-(1-alkyl)-3-methylimidazolium chlorides, with alkyl chains containing 10, 12, and 14 carbons. In addition to investigating relevant micellar properties, we have compared the solution properties of the imidazolium-based surfactants with: 1-(1-alkyl)pyridinium chlorides, and benzyl (2-acylaminoethyl)dimethylammonium chlorides. The former series carries a heterocyclic ring head-group, but does not possess a hydrogen that is as acidic as H2 of the imidazolium ring. The latter series carries an aromatic ring, a quaternary nitrogen and (a hydrogen-bond forming) amide group. The properties of the imidazolium and pyridinium surfactants were determined in the temperature range from 15 to 75°C. The techniques employed were conductivity, isothermal titration calorimetry, and static light scattering. The results showed the important effects of the interactions in the interfacial region on the micellar properties over the temperature range studied.     

Fluorescent nanoparticles of chitosan complex for real-time monitoring drug release

New types of fluorescent nanoparticles (FNPs) were prepared through ionic self-assembly of anthracene derivative and chitosan for applications as drug delivery carriers with real-time monitoring of the process of drug release. Because of the presence of the hydrophilic groups, these FNPs showed excellent dispersion and stability in aqueous solution. The structure and properties of the FNPs were investigated by using means of (1)H NMR, FTIR, SEM, dynamic light scattering (DLS), and so on. The potential practical applications as drug delivery carriers for real-time detection of the drug release process were demonstrated using Nicardipine as a model drug. Upon loading the drug, the strong blue fluorescence of FNPs was quenched due to electron transfer and fluorescence resonance energy transfer (FRET). With release of drug in vitro, the fluorescence was recovered again. The relationship between the accumulative drug release of FNPs and the recovered fluorescence intensity has been established. Such FNPs may open up new perspectives for designing a new class of detection system for monitoring drug release.     

Reentrant morphological transitions in copolymer micelles with pH-sensitive corona

In contrast to self-assembled aggregates of conventional ionic (including polymeric) surfactants the equilibrium micelles of diblock copolymer with a pH-sensitive polyelectrolyte block can exhibit two inverse sequences of morphological transitions triggered by an increase in solution salinity. The direct sequence of the sphere-cylinder-lamella transitions is similar to that for the copolymer with a strongly dissociating ionic block and occurs at a high salt concentration in solution. The abnormal reversed sequence of the lamella-cylinder-sphere transitions is predicted to occur at relatively low ionic strength in solution. The origin of the reentrant transitions is coupling between aggregation and ionization in copolymer micelles.     

Paramagnetic surface active ionic liquids: synthesis,properties, and applications

Paramagnetic surface active ionic liquids (PMSAILs) classify task-specific ionic liquids with magnetic properties by incorporating metal into the cationic or anionic part of the ionic liquid. Paramagnetic ionic liquids had long-chain either in cations or anions and showed excellent surface activity and magnetic properties without any need for the magnetic nanoparticles. These PMSAILs have inherent unique ionic liquid properties and self-assembled into various nano-aggregates such as micelles, vesicles, rod-like micelles, and etc., by modification in the structure of cations or anions. PMSAILs provide stimuli-responsive properties, which is one of the essential aspects of targeted applications. The appropriate functional tunability of anions and cations in PMSAILs leads to various multifaceted chemical and biological applications. A new emerging trend in PMSAIL research is hybridization with flexible materials. This review will mainly deal with the synthesis, characterization, and brief history of PMSAILs and their potential advantages in the various applications in micellar catalysis, purification and separation of biomolecules, compaction and decompaction of DNA, drug delivery, and other biomedical applications.     

Biomacromolecules in microgels — Opportunities and challenges for drug delivery

This brief review aims at providing some illustrative examples on the interaction between microgels and biological macromolecules, with special focus on peptides and proteins, as well as current applications of such systems in drug delivery. In doing so, novel insights on factors affecting peptide/protein incorporation to, distribution within, and release from, sparsely cross-linked microgels are addressed, including effects of network charge and cross-linking density, as well as peptide/protein length/size, charge (distribution), and hydrophobicity. Effects of ambient conditions are also illustrated, with special focus on pH and ionic strength. Notably, factors precluding the application of microgel systems in biomacromolecular drug delivery, e.g., shell formation and incomplete drug release, are discussed, together with challenges and opportunities of these effects in the application of biomacromolecule/microgel systems in drug delivery.     

Advances in Targeting Drug Biological Carriers for Enhancing Tumor Therapy Efficacy

Chemotherapy drugs continue to be the main component of oncology treatment research and have been proven to be the main treatment modality in tumor therapy. However, the poor delivery efficiency of cancer therapeutic drugs and their potential off-target toxicity significantly limit their effectiveness and extensive application. The recent integration of biological carriers and functional agents is expected to camouflage synthetic biomimetic nanoparticles for targeted delivery. The promising candidates, including but not limited to red blood cells and their membranes, platelets, tumor cell membrane, bacteria, immune cell membrane, and hybrid membrane are typical representatives of biological carriers because of their excellent biocompatibility and biodegradability. Biological carriers are widely used to deliver chemotherapy drugs to improve the effectiveness of drug delivery and therapeutic efficacy in vivo, and tremendous progress is made in this field. This review summarizes recent developments in biological vectors as targeted drug delivery systems based on microenvironmental stimuli-responsive release, thus highlighting the potential applications of target drug biological carriers. The review also discusses the possibility of clinical translation, as well as the exploitation trend of these target drug biological carriers.     

Synthesis and solution properties of ionic liquid-type polysiloxane bola surfactants

Three novel ionic liquid (IL)-type polysiloxane bola surfactants (ATPS-MA, ATPS-EA, and ATPS-PA) were designed and synthesized using a two-step method. Their chemical structures were characterized by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopy. Their surface activity and aggregation behavior in aqueous solution were systematically investigated by surface tension measurements, transmission electron microscopy (TEM), and dynamic light scattering (DLS). Surface activity measurement results indicated that the γ_CMC of the three IL-type polysiloxane surfactants are under 25 mN m^?1, and much lower than those of conventional IL hydrocarbon bola surfactants due to the introduction of siloxane group at the end of the hydrophobic chains. TEM and DLS analyses results indicated that the three surfactants can self-assemble into spherical micelles with a range from 50 to 300?nm, indicating potential uses as model systems for biomembranes and vehicles for drug delivery.     

聚合物纳米药物载体的研究进展

近年来, 大量研究结果表明纳米技术可显著提高传统药物的疾病治疗效果, 并在生物医学领域引起了广泛关注. 迄今, 多种聚合物纳米体系已被研发并用于药物的靶向递送. 随着纳米技术的不断发展, 各类生物微环境响应的功能基团也被应用于构筑新型药物载体, 以提高患病部位的药物富集及减少药物的毒副作用. 聚合物纳米药物载体在癌症治疗、 代谢类疾病治疗及抗菌等方面展现出巨大潜力. 本文系统评述了聚合物纳米药物载体的最新研究进展及在生物医药方面的应用.