Qilu Zhang

Electrospun fibers for oil–water separation

The increasing worldwide oil pollution intensifies the needs for new techniques of separation of oil from oily water. Separation by the use of electrospun fibers with selective oil/water absorption is a relatively new but highly promising technique. Owing to their highly specific surface areas, interconnected nanoscale pore structures and the potential to incorporate active chemistry on a nanoscale surface, electrospun fibers have become a promising versatile platform for the separation of oil/water mixtures and emulsions. In this review, after a short introduction to the imperative for oil/water separation and electrospinning technique, we will focus on superhydrophobic/superoleophilic electrospun fibers for oil/water separation, including the preparation of electrospun fibers with superhydrophobic/superoleophilic surfaces, and superhydrophobic/superoleophilic fibrous membranes for oil absorption and oil filtration. Further, superoleophobic/superhydrophilic electrospun fibers and their application for oil–water separation will be discussed as well. Finally, conclusions about this review will be presented while addressing remaining problems and future challenges.

Dual pH- and temperature-responsive RAFT-based block co-polymer micelles and polymer–protein conjugates with transient solubility

Via a smart combination of temperature-responsive and acid labile acetal monomers, copolymers are obtained with a la carte lower critical solution temperature behavior. RAFT copolymerization of these monomers using, respectively, a PEG-functionalized or amine-reactive NHS-functionalized chain transfer agent allows designing of micelles and polymer–protein conjugates with transient solubility properties within a physiologically relevant window.

A triple thermoresponsive schizophrenic diblock copolymer

This article describes a new class of triple thermoresponsive ‘schizophrenic’ diblock copolymer that undergoes transitions from conventional micelles (or vesicles) via unimers to reverse micelles (or vesicles) and finally to a precipitated state upon heating. The various transition temperatures of this copolymer could be well controlled by the concentration of trivalent anion and pH that control the upper critical solution temperature of the poly(dimethylaminoethyl methacrtylate) (PDMAEMA) block or the type of poly(methoxy oligoethylenegylol methacrylate) (PmOEGA) to vary the lower critical solution temperature.

Degradable ketal-based block copolymer nanoparticles for anticancer drug delivery: a systematic evaluation.

Low solubility of potent (anticancer) drugs is a major driving force for the development of noncytotoxic, stimuli-responsive nanocarriers, including systems based on amphiphilic block copolymers. In this regard, we investigated the potential of block copolymers based on 2-hydroxyethyl acrylate (HEA) and the acid-sensitive ketal-containing monomer (2,2-dimethyl-1,3-dioxolane-4-yl)methyl acrylate (DMDMA) to form responsive drug nanocarriers. Block copolymers were successfully synthesized by sequential reversible addition-fragmentation chain transfer (RAFT) polymerization, in which we combined a hydrophilic poly(HEA)x block with a (responsive) hydrophobic poly(HEAm-co-DMDMAn)y copolymer block. The DMDMA content of the hydrophobic block was systematically varied to investigate the influence of polymer design on physicochemical properties and in vitro biological performance. We found that a DMDMA content higher than 11 mol % is required for self-assembly behavior in aqueous medium. All particles showed colloidal stability in PBS at 37 °C for at least 4 days, with sizes ranging from 23 to 338 nm, proportional to the block copolymer DMDMA content. Under acidic conditions, the nanoparticles decomposed into soluble unimers, of which the decomposition rate was inversely proportional to the block copolymer DMDMA content. Flow cytometry and confocal microscopy showed dose-dependent, active in vitro cellular uptake of the particles loaded with hydrophobic octadecyl rhodamine B chloride (R18). The block copolymers showed no intrinsic in vitro cytotoxicity, while loaded with paclitaxel (PTX), a significant decrease in cell viability was observed comparable or better than the two commercial PTX nanoformulations Abraxane and Genexol-PM at equal PTX dose. This systematic approach evaluated and showed the potential of these block copolymers as nanocarriers for hydrophobic drugs.

Polymer-protein conjugation via a ‘grafting to’ approach – a comparative study of the performance of protein-reactive RAFT chain transfer agents

Efficient polymer-protein conjugation is a crucial step in the design of many therapeutic protein formulations including nanoscopic vaccine formulations, antibody-drug conjugates and to enhance the in vivo behaviour of proteins. Here we aimed at preparing well-defined polymers for conjugation to proteins by reversible addition–fragmentation chain transfer (RAFT) polymerization of both acrylates and methacrylamides with protein-reactive chain transfer agents (CTAs). These RAFT agents contain either a N-hydroxysuccinimide (NHS) or pentafluorophenyl (PFP) ester moiety that can be conjugated to lysine residues, and alternatively a maleimide (MAL) or pyridyl disulfide (PDS) moiety that can be conjugated to cysteine residues. Efficiency of the bioconjugation of these polymers to bovine and avian serum albumin was investigated as a function of stoichiometry, polymer molecular weight and the presence of reducing agents. A large molar excess of polymer was required to obtain an acceptable degree of protein conjugation. However, protein modification with N-succinimidyl-S-acetylthiopropionate (SATP) to introduce sulfhydryl groups onto primary amines, significantly increased conjugation efficiency with MAL- and PDS-containing polymers.

Thermoresponsive polymers with lower critical solution temperature: from fundamental aspects and measuring techniques to recommended turbidimetry conditions

Thermoresponsive polymers that undergo reversible phase transition by responding to an environmental temperature change, in particular polymers showing lower critical solution temperature (LCST), are frequently used as smart materials that have found increasing applications. Recently, there has been a rapid growth in interest on LCST polymers and many new research groups are entering the field from a wide range of application areas. While it is great to see more researchers working on LCST polymers, the downside of this rapid growth is that the fundamentals of the LCST phase transition behavior are not always clearly known and respected. Hence, this focus article provides a systematic discussion of the key aspects of the LCST behavior of polymers starting from fundamentals of LCST behavior to practical determination of cloud point temperature (Tcp). Finally, we offer a basic set of recommended measuring conditions for determination of Tcp (10 mg mL−1; 0.5 °C min−1; 600 nm) to facilitate the comparison of the LCST behavior and Tcp values of polymers developed and studied in different laboratories around the globe, which is nowadays nearly impossible since various techniques and parameters are being utilized for the measurements. It should be noted that these recommended conditions serve as a robust tool for turbidimetry, which is one out of the many characterization techniques one should utilize to fully understand LCST behavior of polymers.

Tuning the LCST and UCST Thermoresponsive Behavior of Poly( N,N -dimethylaminoethyl methacrylate) by Electrostatic Interactions with Trivalent Metal Hexacyano Anions and Copolymerization

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) has been reported to show both upper critical solution temperature (UCST) and lower critical solution temperature (LCST) behavior in presence of trivalent metal hexacyano anions, which is attractive for the development of smart materials. In this communication, the influence of the double thermoresponsive behavior of PDMAEMA driven by electrostatic interactions is investigated by comparing systems with [Co(CN)6 ](3-) , [Fe(CN)6 ](3-) , and [Cr(CN)6 ](3-) as trivalent anions. Furthermore, tuning of double thermoresponsive behavior of PDMAEMA by incorporating hydrophilic or hydrophobic comonomers is also discussed in the presence of [Fe(CN)6 ](3-) as trivalent ion.

Acid‐Labile Thermoresponsive Copolymers That Combine Fast pH‐Triggered Hydrolysis and High Stability under Neutral Conditions

Biodegradable polymeric materials are intensively used in biomedical applications. Of particular interest for drug-delivery applications are polymers that are stable at pH 7.4, that is, in the blood stream, but rapidly hydrolyze under acidic conditions, such as those encountered in the endo/lysosome or the tumor microenvironment. However, an increase in the acidic-degradation rate of acid-labile groups goes hand in hand with higher instability of the polymer at pH 7.4 or during storage, thus posing an intrinsic limitation on fast degradation under acidic conditions. Herein, we report that a combination of acid-labile dimethyldioxolane side chains and hydroxyethyl side chains leads to acid-degradable thermoresponsive polymers that are quickly hydrolyzed under slightly acidic conditions but stable at pH 7.4 or during storage. We ascribe these properties to high hydration of the hydroxy-containing collapsed polymer globules in conjunction with autocatalytic acceleration of the hydrolysis reactions by the hydroxy groups.

Core–sheath structured electrospun nanofibrous membranes for oil–water separation

In recent years, both the increasing frequency of oil spill accidents and the urgency to deal seriously with industrial oil-polluted water, encouraged material scientists to design highly efficient, cost effective oil–water separation technologies. We report on electrospun nanofibrous membranes which are composed of core–sheath structured cellulose-acetate (CA)–polyimide (PI) nanofibers. On the surface of the CA–PI fibers a fluorinated polybenzoxazine (F-PBZ) functional layer, in which silica nanoparticles (SNPs) were incorporated, has been applied. Compared with F-PBZ/SNP modified CA fibers reported before for the separation of oil from water, the PI-core of the core–shell F-PBZ/SNP/CA–PI fibers makes the membranes much stronger, being a significant asset in their use. Nanofibrous membranes with a tensile strength higher than 200 MPa, a high water contact angle of 160° and an extremely low oil contact angle of 0° were obtained. F-PBZ/SNP/CA–PI membranes seemed very suitable for gravity-driven oil–water separation as fast and efficient separation (>99%) of oil from water was achieved for various oil–water mixtures. The designed core–sheath structured electrospun nanofibrous membranes may become interesting materials for the treatment of industrial oil-polluted water.

RAFT polymerization of 4-vinylphenylboronic acid as the basis for micellar sugar sensors

Well-defined homo and mPEGylated block (co)polymers of the commercially available unprotected 4-vinylphenylboronic acid (4-VBA) monomer are reported based on reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymerization kinetics are studied in detail for homo and block (co)polymerizations with different chain transfer agents (CTAs) to optimize the preparation of well-defined polymer structures, eventually leading to comparatively low dispersities (Đ ≤ 1.25). Subsequently, block (co)polymers with methoxy poly(ethylene glycol) mPEG-b-P(4-VBA) are prepared using a mPEG-functionalized CTA. The formed block copolymer mPEG114 -b-P(4-VBA)30 is demonstrated to be pH and glucose responsive as its micellization behavior is dictated by pH as well as the presence of glucose. The glucose-responsive pH window of mPEG114 -b-P(4-VBA)30 is found to be pH 9-10 based on the DLS and TEM measurement.