Angular-Independent Photonic Pigments via the Controlled Micellization of Amphiphilic Bottlebrush Block Copolymers

Photonic materials with angular-independent structural color are highly desirable because they offer the broad viewing angles required for application as colorants in paints, cosmetics, textiles, or displays. However, they are challenging to fabricate as they require isotropic nanoscale architectures with only short-range correlation. Here, porous microparticles with such a structure are produced in a single, scalable step from an amphiphilic bottlebrush block copolymer. This is achieved by exploiting a novel “controlled micellization” self-assembly mechanism within an emulsified toluene-in-water droplet. By restricting water permeation through the droplet interface, the size of the pores can be precisely addressed, resulting in structurally colored pigments. Furthermore, the reflected color can be tuned to reflect across the full visible spectrum using only a single polymer (M_n = 290 kDa) by altering the initial emulsification conditions. Such “photonic pigments” have several key advantages over their crystalline analogues, as they provide isotropic structural coloration that suppresses iridescence and improves color purity without the need for either refractive index matching or the inclusion of a broadband absorber.     

Colloid-chemical properties of polymeric complexes based on polycarboxylic acids and polyacrylamide

Colloid-chemical properties of polymeric complexes based on polyacrylic acid, polymethacrylic acid, and copolymer of methacrylic acid and pinene with polyacrylamide in diluted aqueous solutions have been investigated. The synthesis of the copolymer of methacrylic acid and pinene, which is more hydrophobic than polyacrylic and polymethacrylic acids, is described. With the addition of polyacrylamide, macromolecules of polycarboxylic acids in aqueous solutions interact by means of hydrogen bonds between carboxylic and amide groups. Intermolecular interactions depend on conformational mobility of linear parts of the macromolecular chains and determine the complexation ability. The effect of the hydrophobicity of the initial polymers and their ratio on the properties (viscosity, pH and surface tension) of the polymeric complexes is discussed. The stability of the complexes formed depends on the presence and quantity of hydrophobic groups in the macromolecules of the polyacids.     

Aptamers and Their Applications in Nanomedicine

Aptamers are composed of short RNA or single‐stranded DNA sequences that, when folded into their unique 3D conformation, can bind to their targets with high specificity and affinity. Although functionally similar to protein antibodies, oligonucleotide aptamers offer several advantages over protein antibodies in biomedical and clinical applications. Through the enhanced permeability and retention effect, nanomedicines can improve the therapeutic index of a treatment and reduce side effects by enhancing accumulation at the disease site. However, this targets tumors passively and, thus, may not be ideal for targeted therapy. To construct ligand‐directed “active targeting” nanobased delivery systems, aptamer‐equipped nanomedicines have been tested for in vitro diagnosis, in vivo imaging, targeted cancer therapy, theranostic approaches, sub‐cellular molecule detection, food safety, and environmental monitoring. This review focuses on the development of aptamer‐conjugated nanomedicines and their application for in vivo imaging, targeted therapy, and theranostics.     

Functional Macromolecule‐Enabled Colloidal Synthesis: From Nanoparticle Engineering to Multifunctionality

The synthesis of well‐defined inorganic colloidal nanostructures using functional macromolecules is an enabling technology that offers the possibility of fine‐tuning the physicochemical properties of nanomaterials and has contributed to a broad range of practical applications. The utilization of functional reactive polymers and their colloidal assemblies leads to a high level of control over structural parameters of inorganic nanoparticles that are not easily accessible by conventional methods based on small‐molecule ligands. Recent advances in polymerization techniques for synthetic polymers and newly exploited functions of natural biomacromolecules have opened up new avenues to monodisperse and multifunctional nanostructures consisting of integrated components with distinct chemistries but complementary properties. Here, the evolution of colloidal synthesis of inorganic nanoparticles is revisited. Then, the new developments of colloidal synthesis enabled by functional macromolecules and practical applications associated with the resulting optical, catalytic, and structural properties of colloidal nanostructures are summarized. Finally, a perspective on new and promising pathways to novel colloidal nanostructures built upon the continuous development of polymer chemistry, colloidal science, and nanochemistry is provided.     

Scaffolds for drug delivery,part I: electrospun porous poly(lactic acid) and poly(lactic acid)/poly(ethylene oxide) hybrid scaffolds

This is the first in a series of papers, focused on the development of a biodegradable, controlled, and potentially targeted drug delivery system. In this paper, we describe the production of highly porous biodegradable fibrous structures suitable for biomedical applications and as a matrix for drug delivery. Two structures are described below. The first structure is composed of electrospun poly(lactic acid) (PLA) fibers and is unique due to (1) the uniformity if its constitute fibers’ diameter, (2) consistent surface pore dimensions of each fiber, (3) the use of only a single solvent, (4) interior nano-size porosity throughout each individual fiber, and (5) the independency of surface pore dimensions on fiber diameter. The produced matrix will be further impregnated with cargo loaded nanoparticles—Red clover necrotic mosaic virus (RCNMV)—to achieve a controlled drug delivery system (described in Part III) for cancer treatments. Such a structure can also be used as tissue engineering scaffolds and filter media. The second electrospun structure has enhanced hydrophilicity compared to PLA matrix and is formed by blending poly(lactic acid)/poly(ethylene oxide) (PEO) polymers. The incorporation of PEO in the matrix introduces preferable sites for aqueous compounds to be attached to while retaining the overall structural integrity and porous morphology. It is hypothesized that the existence of alternative hydrophilic and hydrophobic segments in the structure may reduce post-implantation complications such as platelet adhesion.     

Lepidocrocite-like ferrititanate nanosheets and their full exfoliation with quaternary ammonium compounds

Efficient methods for the synthesis of layered structure nanomaterials (nanosheets), their complete exfoliation (delamination) into the layers of atomic thickness and design of organic–inorganic nanohybrids present important stages toward development of improved polymer-based nanocomposites and pillared heterostructures with potential application in purification technologies such as photocatalysis. A rapid and efficient exfoliation process of protonated layered ferrititanates with lepidocrocite-like structure and formation of organic–inorganic nanohybrids is performed starting from the nanosheets composed of only a few host layers and nanometric lateral dimensions using quaternary ammonium compounds. These nanosheets are initially synthesized from a highly abundant precursor through an alkaline hydrothermal route. We demonstrated that dimethyldioctadecylammonium cations strongly interact with the exfoliated single host layers (0.75 nm thick) providing thermal stability (~ 500 °C) to the as-prepared organic–inorganic nanohybrid over the temperature range commonly applied for the processing of thermoplastic nanocomposites.     

Synthesis of nanomedicines by nanohybrids conjugating ginsenosides with auto-targeting and enhanced MRI contrast for liver cancer therapy

A new methodology has been developed with conjugating nanoparticles (NPs) with an active ingredient of Chinese herbs for nanomedicines with auto-targeting and enhanced magnetic resonance imaging (MRI) for liver cancer therapy. Fe@Fe₃O₄ NPs are first synthesized via the programed microfluidic process, whose surfaces are first modified with –NH₂ groups using a silane coupling technique that uses (3-aminopropyl)trimethoxysilane (APTMS) as the coupling reagent and are subsequently activated by the bifunctional amine-active cross-linker [e.g. disuccinimidyl suberate (DSS)]. The model medicines of ginsenosides pre-activated by APTMS are further cross-linked with activated NPs, forming the desired nanomedicines (Nano-Fe-GSS). Sizes and structures of Fe@Fe₃O₄ NPs were characterized by transmission electron microscopy and X-ray diffraction, revealing that their core-shell structures consist of amorphous boron doped Fe cores and partial crystalline Fe₃O₄ shells. The accomplishment of coupling reactions in the final nanomedicines is confirmed by the characterization of the composition of NPs and Nano-Fe-GSS via X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectroscopy. The nanoparticles’ effects as MRI contrast agents are further investigated by comparing the T₂ weighted spin echo imaging (T2WI) in livers before and after intravenous injection and intragastric administration of nanomedicines. The results indicate that these nanomedicines possess enhanced MRI effects. Investigation of the toxicity and metabolism of Nano-Fe-GSS suggests that they are safe to related vital organs. The results provide an efficient alternative route to synthesize desired multi-functional nanomedicines based on NPs and the active ingredients of Chinese herbs, which can promote their potential synergistic effects in anti-tumor therapy.     

超支化研究进展及应用

超支化聚合物以其独特的结构和性能及可实现规模化生产而成为研究热点之一。本文主要介绍了超支化聚合物的合成方法、应用及最新研究进展,旨在加深人们对该领域的了解,从而加速该领域的发展。     

Colloidal Polymer-Templated Formation of Inorganic Nanocrystals and their Emerging Applications

Inorganic nanocrystals possess unique physicochemical properties compared to their bulk counterparts. Stabilizing agents are commonly used for the preparation of inorganic nanocrystals with controllable properties. Particularly, colloidal polymers have emerged as general and robust templates for in situ formation and confinement of inorganic nanocrystals. In addition to templating and stabilizing inorganic nanocrystals, colloidal polymers can tailor their physicochemical properties such as size, shape, structure, composition, surface chemistry, and so on. By incorporating functional groups into colloidal polymers, desired functions can be integrated with inorganic nanocrystals, advancing their potential applications. Here, recent advances in the colloidal polymer-templated formation of inorganic nanocrystals are reviewed. Seven types of colloidal polymers, including dendrimer, polymer micelle, stare-like block polymer, bottlebrush polymer, spherical polyelectrolyte brush, microgel, and single-chain nanoparticle, have been extensively applied for the synthesis of inorganic nanocrystals. Different strategies for the development of these colloidal polymer-templated inorganic nanocrystals are summarized. Then, their emerging applications in the fields of catalysis, biomedicine, solar cells, sensing, light-emitting diodes, and lithium-ion batteries are highlighted. Last, the remaining issues and future directions are discussed. This review will stimulate the development and application of colloidal polymer-templated inorganic nanocrystals.     

超支化聚合物合成的研究进展

超支化聚合物是一类具有高度支化结构的体型大分子,其独特的结构赋予其具有不同于传统线性聚合物的性能,显示出广阔的应用前景.超支化聚合物的合成是超支化聚合物研究的重要内容,合成方法对超支化聚合物的结构和性能有重要影响.对该领域的最新研究进展进行了归纳介绍,其中主要涉及传统的缩聚聚合、活性聚合、离子聚合、开环聚合以及一些新型的聚合反应,同时论述了各种合成方法的优点和局限性.     

Nanoparticle Regrowth Enhances Photoacoustic Signals of Semiconducting Macromolecular Probe for In Vivo Imaging

Smart molecular probes that emit deep‐tissue penetrating photoacoustic (PA) signals responsive to the target of interest are imperative to understand disease pathology and develop innovative therapeutics. This study reports a self‐assembly approach to develop semiconducting macromolecular activatable probe for in vivo imaging of reactive oxygen species (ROS). This probe comprises a near‐infrared absorbing phthalocyanine core and four poly(ethylene glycol) (PEG) arms linked by ROS‐responsive self‐immolative segments. Such an amphiphilic macromolecular structure allows it to undergo an ROS‐specific cleavage process to release hydrophilic PEG and enhance the hydrophobicity of the nanosystem. Consequently, the residual phthalocyanine component self‐assembles and regrows into large nanoparticles, leading to ROS‐enhanced PA signals. The small size of the intact macromolecular probe is beneficial to penetrate into the tumor tissue of living mice, while the ROS‐activated regrowth of nanoparticles prolongs the retention along with enhanced PA signals, permitting imaging of ROS during chemotherapy. This study thus capitalizes on stimuli‐controlled self‐assembly of macromolecules in conjunction with enhanced heat transfer in large nanoparticles for the development of smart molecular probes for PA imaging.     

纳米硅胶的仿生合成研究

介绍了硅胶仿生合成中硅前体和有机大分子添加剂的类型及其作用机制,重点讨论了纳米硅胶仿生合成的影响因素.硅前体主要影响硅胶形成的动力学速度,对于一定的硅前体,尤其是有机硅前体,溶液的pH、预水解时间、硅前体的浓度、反应时间、反应温度和搅拌速率等都是控制硅胶产物形成的因素.有机大分子添加剂主要对硅胶的晶核形成和长大起到定向模板的诱导作用,是决定硅胶粒子大小、结构和形态的主要因素,来自生物体或仿生合成的有机聚阳离子或能与硅氧离子形成氢键的聚合物是理想的添加剂类型.反应介质的性质能对有机大分子添加剂的诱导作用产生一定的影响.     

Targeted tumor cell internalization and imaging of multifunctional quantum dot-conjugated immunoliposomes in vitro and in vivo

Targeted drug delivery systems that combine imaging and therapeutic modalities in a single macromolecular construct may offer advantages in the development and application of nanomedicines. To incorporate the unique optical properties of luminescent quantum dots (QDs) into immunoliposomes for cancer diagnosis and treatment, we describe the synthesis, biophysical characterization, tumor cell-selective internalization, and anticancer drug delivery of QD-conjugated immunoliposome-based nanoparticles (QD-ILs). Pharmacokinetic properties and in vivo imaging capability of QD-ILs were also investigated. Freeze-fracture electron microscopy was used to visualize naked QDs, liposome controls, nontargeted QD-conjugated liposomes (QD-Ls), and QD-ILs. QD-ILs prepared by insertion of anti-HER2 scFv exhibited efficient receptor-mediated endocytosis in HER2-overexpressing SK-BR-3 and MCF-7/HER2 cells but not in control MCF-7 cells as analyzed by flow cytometry and confocal microscopy. In contrast, nontargeted QD-Ls showed minimal binding and uptake in these cells. Doxorubicin-loaded QD-ILs showed efficient anticancer activity, while no cytotoxicity was observed for QD-ILs without chemotherapeutic payload. In athymic mice, QD-ILs significantly prolonged circulation of QDs, exhibiting a plasma terminal half-life ( t 1/2) of approximately 2.9 h as compared to free QDs with t 1/2 < 10 min. In MCF-7/HER2 xenograft models, localization of QD-ILs at tumor sites was confirmed by in vivo fluorescence imaging.     

Polymer brushes as active nanolayers for tunable bacteria adhesion

Bacterial biofilm formation on implant surfaces is a frequent reason for the failure of many biomedical devices. Polymer brushes, thin nanolayers constituted of densely grafted macromolecules, are promising candidates to use in many biomedical applications to control attachment of bacteria to a surface. In this work five different polymer brushes were synthesized and tested with respect to their ability to regulate Staphylococcus aureus adhesion. Namely, two mixed brushes [consisting of poly(ethylene glycol) and a positively charged polymers, poly(2-vynil pyridine) or quartenized poly(2-vynil pyridine)] are investigated along with one-component brushes of the respective polymers. Bacterial adhesion was regulated over two orders of magnitude via altering the polymer brush composition.     

Polysaccharide-Based Stimulus-Responsive Nanomedicines for Combination Cancer Immunotherapy

Cancer immunotherapy is a promising antitumor approach, whereas nontherapeutic side effects, tumor microenvironment (TME) intricacy, and low tumor immunogenicity limit its therapeutic efficacy. In recent years, combination immunotherapy with other therapies has been proven to considerably increase antitumor efficacy. However, achieving codelivery of the drugs to the tumor site remains a major challenge. Stimulus-responsive nanodelivery systems show controlled drug delivery and precise drug release. Polysaccharides, a family of potential biomaterials, are widely used in the development of stimulus-responsive nanomedicines due to their unique physicochemical properties, biocompatibility, and modifiability. Here, the antitumor activity of polysaccharides and several combined immunotherapy strategies (e.g., immunotherapy combined with chemotherapy, photodynamic therapy, or photothermal therapy) are summarized. More importantly, the recent progress of polysaccharide-based stimulus-responsive nanomedicines for combination cancer immunotherapy is discussed, with the focus on construction of nanomedicine, targeted delivery, drug release, and enhanced antitumor effects. Finally, the limitations and application prospects of this new field are discussed.     

New Triblock Copolymer Templates,PEO‐PB‐PEO,for the Synthesis of Titania Films with Controlled Mesopore Size,Wall Thickness,and Bimodal Porosity

The synthesis and properties of a series of new structure‐directing triblock copolymers with PEO‐PB‐PEO structure (PEO = poly(ethylene oxide) and PB = polybutadiene) and their application as superior pore‐templates for the preparation of mesoporous titania coatings are reported. Starting from either TiCl₄ or from preformed TiO₂ nanocrystalline building blocks, mesoporous crystalline titanium oxide films with a significant degree of mesoscopic ordered pores are derived, and the pore size can be controlled by the molecular mass of the template polymer. Moreover, the triblock copolymers form stable micelles already at very low concentration, i.e., prior to solvent evaporation during the evaporation‐induced self‐assembly process (EISA). Consequently, the thickness of pore walls can be controlled independently of pore size by changing the polymer‐to‐precursor ratio. Thus, unprecedented control of wall thickness in the structure of mesoporous oxide coatings is achieved. In addition, the micelle formation of the new template polymers is sufficiently distinct from that of typical commercial PPO‐PEO‐PPO polymers (Pluronics; PPO = poly(propylene oxide)), so that a combination of both polymers facilitates bimodal porosity via dual micelle templating.     

原子转移自由基聚合在超支化大分子合成中的应用进展

超支化聚合物是一类具有不同于线性聚合物性质的新型高分子材料,原子转移自由基聚合(ATRP)作为一种活性可控聚合方法,在超支化聚合物合成领域发挥着重要的作用。ATRP在Cu(I)催化体系下不仅可以催化AB~*型单体生成超支化聚合物,而且还可以多官能团的大分子为引发剂,生成具有"核-壳"结构的两亲性共聚物或其它特殊结构大分子。文中主要介绍了近年来采用ATRP法合成的不同结构超支化聚合物,并对ATRP在超支化大分子合成中的应用前景进行了展望。     

可控活性自由基聚合制备端基官能化聚合物研究进展

端基官能化聚合物是指那些在聚合物末端或悬垂端含有活性官能团的聚合物。它们可发挥交联剂或扩链剂的作用,从而制备出不同结构特点的嵌段聚合物、接枝聚合物、星型、超支化或树状聚合物。文章主要对引发转移终止剂(Iniferter)法、原子转移自由基聚合(ATRP)、氮氧自由基调控聚合(NMRP)和可逆加成-断裂链转移自由基聚合(RAFT)等可控活性自由基聚合方法在制备端基官能化聚合物中的应用进行了介绍。最后对可控活性自由基聚合在功能性聚合物制备中的应用前景进行了展望。     

Tuning structure and properties of graded triblock terpolymer-based mesoporous and hybrid films

Despite considerable efforts toward fabricating ordered, water-permeable, mesoporous films from block copolymers, fine control over pore dimensions, structural characteristics, and mechanical behavior of graded structures remains a major challenge. To this end, we describe the fabrication and performance characteristics of graded mesoporous and hybrid films derived from the newly synthesized triblock terpolymer, poly(isoprene-b-styrene-b-4-vinylpyridine). A unique morphology, unachievable in diblock copolymer systems, with enhanced mechanical integrity is evidenced. The film structure comprises a thin selective layer containing vertically aligned and nearly monodisperse mesopores at a density of more than 10(14) per m(2) above a graded macroporous layer. Hybridization via homopolymer blending enables tuning of pore size within the range of 16 to 30 nm. Solvent flow and solute separation experiments demonstrate that the terpolymer films have permeabilities comparable to commercial membranes, are stimuli-responsive, and contain pores with a nearly monodisperse diameter. These results suggest that moving to multiblock polymers and their hybrids may open new paths to produce high-performance graded membranes for filtration, separations, nanofluidics, catalysis, and drug delivery.