Polymer‐Chlorambucil Drug Conjugates: A Dynamic Platform of Anticancer Drug Delivery

Recently, polymer drug conjugates (PDCs) have attracted considerable attention in the treatment of cancer. In this work, a simple strategy has been developed to make PDCs of an antitumor alkylating agent, chlorambucil, using a biocompatible disulphide linker. Chlorambucil‐based chain transfer agent was used to prepare various homopolymers and block copolymers in a controlled fashion via reversible addition–fragmentation chain transfer polymerization. Chlorambucil conjugated block copolymer, poly(polyethylene glycol monomethyl ether methacrylate)‐b‐poly(methyl methacrylate), formed nanoaggregates in aqueous solutions, which are characterized by dynamic light scattering and field emission‐scanning electron microscopy. Finally, the simplicity of the design is exemplified by performing a release study of chlorambucil under reducing condition by using D,L‐dithiothreitol.

     

Highly Ordered Structure Formation in RAFT‐Synthesized PtBOS‐b‐P4VP Diblock Copolymers

Linear poly(4‐tert‐butoxystyrene)‐b‐poly(4‐vinylpyridine) (PtBOS‐b‐P4VP) diblock copolymers are synthesized using reversible addition–fragmentation chain transfer polymerization. The self‐assembly of four different PtBOS‐b‐P4VP diblock copolymers is studied using small‐angle X‐ray scattering and transmission electron microscopy and a number of interesting observations are made. A tBOS₆₂‐b‐4VP₂₈ diblock copolymer with a weight fraction P4VP of 0.21 shows a disordered morphology of P4VP spheres with liquid‐like short‐range order despite an estimated value of of the order of 50. Increasing the length of the 4VP block to tBOS₆₂‐b‐4VP₁₉₉ results in a diblock copolymer with a weight fraction P4VP of 0.66. It forms a remarkably well‐ordered lamellar structure. Likewise, a tBOS₁₄₆‐b‐4VP₁₂₀ diblock copolymer with a weight fraction P4VP of 0.33 forms an extremely well‐ordered hexagonal structure of P4VP cylinders. Increasing the P4VP block of this block copolymer to tBOS₁₄₆‐b‐4VP₁₉₀ with a weight fraction P4VP of 0.44 results in a bicontinuous gyroid morphology despite the estimated strong segregation of . These results are discussed in terms of the architectural dissimilarity of the two monomers, characterized by the presence of the large side group of PtBOS, and the previously reported value of the interaction parameter, , for this polymer pair.

     

Recent Development of Durable and Self‐Healing Surfaces with Special Wettability

Artificial special wetting surfaces have drawn much interest due to their important applications in many fields. Nevertheless, tremendous challenges still remain for the fabrication of wetting surfaces with durable and self‐healing properties. Here, recent progress of durable, self‐healing wetting surfaces is highlighted by discussing the fabrications of several typical wetting surfaces including superhydrophobic surfaces, superamphiphobic surfaces, underwater superoleophobic surfaces, and high hydrophilic antifouling surfaces based on expertise and related research experience. To conclude, some perspectives on the future research and development of these special wetting surfaces are presented.

     

Low‐Temperature Synthesis of Thermoresponsive Diblock Copolymer Nano‐Objects via Aqueous Photoinitiated Polymerization‐Induced Self‐Assembly (Photo‐PISA) using Thermoresponsive Macro‐RAFT Agents

Photoinitiated reversible addition‐fragmentation chain transfer (RAFT) dispersion polymerization of 2‐hydroxypropyl methacrylate is conducted in water at low temperature using thermoresponsive copolymers of 2‐(2‐methoxyethoxy) ethyl methacrylate and oligo(ethylene glycol) methacrylate (M_n = 475 g mol⁻¹) as the macro‐RAFT agent. Kinetic studies confirm that quantitative monomer conversion is achieved within 15 min of visible‐light irradiation (405 nm, 0.5 mW cm⁻²), and good control is maintained during the polymerization. The polymerization can be temporally controlled by a simple “ON/OFF” switch of the light source. Finally, thermoresponsive diblock copolymer nano‐objects with a diverse set of complex morphologies (spheres, worms, and vesicles) are prepared using this particular formulation.

     

Amphiphilic Copolymers of Polyfluorene Methacrylates Exhibiting Tunable Emissions for Ink‐Jet Printing

Functionalized polyfluorene receives more and more attention due to its wide applications. Here, the syntheses of three novel polyfluorene‐based methacrylate macromonomers exhibiting a vast flexibility for further applications are reported. Their emissions strongly depend on the end groups and thus the macromonomers provide blue, green, and red emissions simultaneously with the same excitation light of 365 nm. Their well‐defined copolymers with 2‐(dimethylamino) ethyl methacrylate via reversible addition‐fragmentation chain transfer polymerization are investigated in detail. These copolymers exhibit high quantum yields in solid film (up to 0.8), and self‐assemble into photoluminescent nanoparticles in aqueous solutions with pure blue, green, and red emissions. By simply mixing them, perfect white light emission with high quality is obtained. These aqueous nanoparticles solutions are ready for ink‐jet printing to produce exquisite bright and colorful fluorescent pictures.

     

Self‐Assembly of Amphiphilic Anthracene‐Functionalized β‐Cyclodextrin (CD‐AN) through Multi‐Micelle Aggregation

Multi‐micelle aggregation (MMA) mechanism is widely acknowledged to explicate large spherical micelles self‐assembly, but the process of MMA during self‐assembly is hard to observe. Herein, a novel kind of strong, regular microspheres fabricated from self‐assembly of amphiphilic anthracene‐functionalized β‐cyclodextrin (CD‐AN) via Cu(I)‐catalyzed azide‐alkyne click reactions is reported. The obtained CD‐AN amphiphiles can self‐assemble in water from primary core–shell micelles to secondary aggregates with the diameter changing from several tens nm to around 600–700 nm via MMA process according to the images of scanning electron microscopy, transmission electron microscopy, and atomic force microscopy as well as the dynamic light scattering measurements, followed by further crosslinking through photo‐dimerization of anthracene. What merits special attention is that such photo‐crosslinked self‐assemblies are able to disaggregate reversibly into primary nanoparticles when changing the solution conditions, which is benefited from the designed regular structure of CD‐AN and the rigid ranging of anthracene during assembly, thus confirming the process of MMA.

     

Multiblock Copolymer‐Based Dual Dynamic Disulfide and Supramolecular Crosslinked Self‐Healing Networks

A new multiblock copolymer self‐healing strategy is reported that centers on the synthesis of block copolymers designed with different self‐healing motifs incorporated into individual blocks. As a proof of concept, a novel pentablock copolymer (ABCBA) consisting of a poly(ethylene glycol) middle block and self‐healable symmetric blocks of a polymethacrylate with pendant disulfide linkages and carboxylic acids is synthesized by a combination of consecutive controlled radical polymerization with hydrolytic cleavage. Disulfide exchange reactions of pendant disulfide linkages and metal–ligand interactions of pendant carboxylic acids with ferric ions allow for the formation of dual crosslinked networks with dynamic disulfide and supramolecular crosslinkages. The resultant networks possessing self‐healing viscoelasticity enable self‐healing on macroscale damages through supramolecular metal–ligand interactions and disulfide exchange reactions at room or moderate temperatures. These preliminary results suggest that the strategy can offer the versatility in the development of multifunctional self‐healable materials in dual or multiple self‐healable mechanisms.

     

A Multiresponsive Amphiphilic Supramolecular Diblock Copolymer Based on Pillar[10]arene/Paraquat Complexation for Rate‐Tunable Controlled Release

Herein, for rate‐tunable controlled release, the authors report a new facile method to prepare multiresponsive amphiphilic supramolecular diblock copolymers via the cooperative complexation between a water‐soluble pillar[10]arene and paraquat‐containing polymers in water. This supramolecular diblock copolymer can self‐assemble into multiresponsive polymeric micelles at room temperature in water. The resultant micelles can be further used in the controlled release of small molecules with tunable release rates depending on the type of single stimulus and the combination of various stimuli.

     

A parametric investigation of the friction performance of PC‐ABS parts processed by FDM additive manufacturing process

The friction performance is an important factor of parts processed by fused deposition modeling (FDM) for various engineering applications. It is one type of failure made of surface contact. The proper use of FDM process parameters can bring a significant reduction in friction and the amount of wear, thereby leading to a reduction in the material waste. To date, very little studies have been performed in this area. This paper investigates the effect of FDM manufacturing parameters on the friction performance of polycarbonate‐acrylonitrile butadiene styrene prototypes processed by FDM using definitive screening design and partial least squares method. The observation of surface morphology was obtained by the scanning electron microscopy to examine the effect of process parameters on the microstructure. The experimental results have shown that layer thickness, air gap, raster angle, and build orientation are the most influential factors affecting the friction performance of FDM manufactured parts. The proposed approach presented in this study provides an impetus to develop analytical modeling and functional relationships between FDM manufacturing parameters and friction performance. Copyright © 2017 John Wiley & Sons, Ltd.     

Sensitive and Selective Fluorescent and Colorimetric Sensor for Ag+ Based on the Supramolecular Self‐Assembly in Semi‐Water

Specific recognition of ultratrace levels of ions in semi‐water using super‐quicker methods is still a challenge for environmental monitoring. Herein we report a fluorescent and colormetric sensor ( ZH ) based on supramolecular self‐assembly, whose structure was destroyed by the addition of ultratrace of silver ions. The process promoted either naked eye visible color changes or fluorescence intensity quenched in conjunction with a wide pH range. Systematic studies revealed very high selectivity (0.07 µmol/L) for silver ions, and other common cations, e.g ., Hg²⁺, Cu²⁺, Cd²⁺, Pb²⁺ had nearly no influence on the sensing behavior. This sensor also served as a multiple use of component in sensing materials by addition of I⁻ into the mixture of ZH and Ag⁺ (about 5 times). What's more, ZH containing filter paper emerged distinct color and fluorescence changes upon exposure to silver (Ag⁺), which could be used as a portable method to undertake field testing for Ag ⁺ .