Association,emulsifying, and solubilization properties of amphiphilic hyperbranched poly(acrylic acid) with short polystyrene stickers

Amphiphilic hyperbranched copolymer chains made of large hyperbranched poly(acrylic acid) cores grafted with short polystyrene stickers (HB‐PAA_n‐g‐PS_{n + 1}) with different n values (n = 1, 10, 47) were well prepared and confirmed by size exclusion chromatography, Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. The study on the interchain association behavior of these amphiphilic chains indicates that larger HB‐(PAA)_n‐g‐(PS)_{n + 1} copolymer chains have a less tendency to undergo interchain association. Moreover, the simple vial‐inversion and rheological experiments show that the apparent critical gel concentration (C_g) decreases with n, but no sol–gel transition was observed for triblock PS‐PAA‐PS even when the concentration is up to 200 g L^?1. Further transmission electron microscopy study of the latex particles prepared with HB‐(PAA)_n‐g‐(PS)_{n + 1} as surfactant reveals that the latex particles are spherical and narrowly dispersed; while the measured latex particle number (N_p) indicates the surfactant efficiency of HB‐(PAA)₄₇‐g‐(PS)₄₈ is poorer than that of triblock PS‐PAA‐PS (n = 1). Finally, pyrene solubilization measurement shows the solubilization efficiency of HB‐(PAA)_n‐g‐(PS)_{n + 1} copolymers decreases with n, consistent with the previous observed interchain association result. The present study demonstrates that both the chain topology and the styrene weight fraction dominates the final solution properties of amphiphilic HB‐(PAA)_n‐g‐(PS)_{n + 1} chains in aqueous solution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 128–138     

Chitosan/Ce(IV) redox polymerization‐based amplification for detection of DNA point mutation

Polymerization‐based signal amplification, a technique developed for use in rapid diagnostic tests, hinges on the ability to localize initiators as a function of interfacial binding events. We report here a new DNA detection method in which polymer growth in redox‐polymerization is used as a means to amplify detection signals. The introduction of biotin‐labeled chitosan (biotin‐CS) with highly dense amino groups into the polymerization amplification as macromolecular reducing agent, beneficially simplifies amplification operation, as well as, provides a large amount of initiation points to improve the sensitivity of detection. DNA hybridization, SA and biotin binding reactions led to the attachment of CS on a solid surface where specific DNA sequences were located. With the addition of the mixture containing monomer AM, crosslinker PEGDA and oxidant CAN onto the CS location, the growth of polymer films was triggered to render the corresponding spots readily distinguishable to the naked eye. Direct visualization of 0.21 fmol target DNA molecules of interest was demonstrated. Non‐small cell lung cancer p53 sequence was further selected as a proof‐of‐principle to detect DNA point mutation. The proposed method exhibited an efficient amplification performance for molecule detection, and paved a new way for visual diagnosis of biomolecules. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1929–1937     

Electrochemical detection of nitrate,nitrite and ammonium for on-site water quality monitoring

This review examines the most recent electrochemical developments for nitrate, nitrite and ammonium detection for on-site water monitoring. There remains a high demand for effective field-based detection of the dissolved inorganic nitrogen (DIN) analytes to aid in mitigating nitrogen loading. Electrochemical approaches show increasing potential to fill this role as advancements in nanotechnology continually improve analytical performance and on-site applicability. However, translating these improvements into the field still faces the resonating challenges of reaching analytical proficiency (selectivity, sensitivity, robustness, stability), practical end-user functionality, minimal matrix interferences and cost effectiveness. Herein, we elaborate on these challenges via a critical evaluation of current studies and examine how realistic the prospects of on-site nitrate, nitrite and ammonium are. We also present recommendations in addressing these gaps to conclude the review.     

Electrochemical Signal Enhancer Fabricated Using Lysine‐rich Peptide for Ultrasensitive Electrochemical DNA Biosensor Analysis

Here we present a novel design of electrochemical signal enhancer to increase the detection sensitivity of electrochemical DNA biosensors. The key element of this enhancer is a lysine‐rich peptide (LRP). Its C‐terminal is conjugated with a planer molecule, being able to intercalate into the base pairs of probe‐target duplexes. The lysine residues of LRP are covalently linked with electrochemical signal indicators, acting as an assembly of electrochemical signal indicators. Experimental results proved the feasibility of the novel design. We have examined the effects of the numbers of lysine residues and the hybridization conditions on the detection sensitivity. The optimization procedures have led to significant sensitivity enhancement, and the LOD (limit of detection) has been determined to be 1.4 amol. This enhancer demonstrates advantages of easy operation, simple instrumentation, and high exemption from environmental influence.     

Synthesis of oligo(spiroketal)s by polycondensation of silyl ethers derived from naturally occurring myo‐inositol with 1,4‐cyclohexanedione

Oligo(spiroketal)s (OSKs) were synthesized from myo‐inositol, a naturally occurring cyclic compound bearing six hydroxyl groups. The successful synthesis of OSKs was achieved using silyl ethers 2 derived from 1,4‐di‐O‐alkylated myo‐inositol 1 as monomers, which underwent polycondensation with 1,4‐cyclohexanedione (CHD) at 0 °C in the presence of trimethylsilyl triflate as a catalyst. Because of the irreversible nature of the condensation reaction of silyl ethers with ketones, the resulting OSKs 7 had higher molecular weights than previously reported OSKs that were obtained by polycondensation of tetraols 1 with CHD, where backward hydrolysis of the ketal functions occurred. In addition, another series of OSKs, 8, were synthesized using silyl ethers 3 derived from 2,5‐di‐O‐alkylated myo‐inositol 6 , which are more symmetric monomers than silyl ethers 2 . Silyl ethers 3 underwent efficient polycondensation with CHD, whereas tetraol 6 did not, demonstrating that the derivation of such tetraols into the corresponding silyl ethers is a powerful strategy to access OSKs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2407–2414     

Switching from linear to cyclic δ‐Polyvalerolactone synthesized via zeolitic imidazolate framework as a catalyst: A promising approach

A series of spray dried zeolitic imidazolate frameworks (ZIFs = ZIF‐8, ZIF‐67, and Zn/Co‐ZIF) are used as a catalyst for the bulk ring‐opening polymerization of δ‐valerolactone without any co‐catalyst to generate polyvalerolactone. Interestingly, using the same catalyst under the same reaction conditions could manipulate the structure of the product polymer, and thus its physical properties. Thus, using a dried substrate leads to the formation of the cyclic polymer while a linear polymer was formed on using the commercially available substrate. An activated monomer mechanism has been suggested where the propagating zinc alkoxide undergoes an intramolecular transesterification to release cyclic or linear polyvalerolactone. The ROP of δ‐VL without drying shows that the polymeric zwitterions have little tendency to cyclize in the presence of moisture. At 140 °C, ZIF‐8 shows a superior catalytic activity resulting in the production of cyclic polyvalerolactone having a high molecular weight as compared to ZIF‐67 or Zn/Co‐ZIF due to the presence of highly active sites. The catalyst could be recycled and reused without any significant loss of catalytic activity.     

Photopolymerization of enzymatically synthesized methacrylated poly(caprolactone) with poly(ethylene glycol) macromonomer

Polycaprolactone (PCL) based α,ω-methacrylated macromonomer (DMPCL) was synthesized via enzymatic ring-opening polymerization (eROP) by using Novozyme 435 as the enzyme immobilized catalyst. DMPCL was further photopolymerized with monofunctional poly(ethylene glycol) methyl ether methacrylate (PEGMA-950) macromonomer and trimethylolpropane triacrylate (TMPTA) as tri-functionalized crosslinking agent in glass vials when CHCl₃ was the solvent and Irgacure 819 was the photoinitiator. Ultraviolet (UV) Light Emitting Diode (LED) bulbs enabled photoinduced reactions at room temperature with low heat generation and high reaction efficiency. The obtained gels were characterized with Fourier Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC). DMPCL participated as an effective crosslinking agent in the photopolymerization of PEGMA-950. Combined usage of DMPCL and PEGMA-950 resulted in significantly more effective polymerization than the separate photopolymerizations of these macromonomers.     

Electrochemical sensors for environmental gas analysis

The application of electrochemical sensors for measurement of concentration of pollutant gases in air in the part-per-billion (10⁹) range is reviewed. Performance-limiting factors, particularly the effects of extremes and of relatively rapid changes in ambient temperature and humidity, are noted. Variations in composition of the electrolyte in the meniscus at the electrode–gas interface and instability of the solid–liquid–gas contact line, causing important variations in current due to background electrode reactions, are deduced and suggested as the reason for the performance limitations. Suggestions are made for mitigation through instrument design.