Control of thermoresponsivity of biocompatible poly(trimethylene carbonate) with direct introduction of oligo(ethylene glycol) under various circumstances

Poly(trimethylene carbonate) (PTMC) is a well‐known biodegradable polymer with good biocompatible properties which make it suitable for biomedical applications. Poly(5‐[2‐{2‐(2‐methoxyethoxy)ethyoxy}‐ethoxymethyl]‐5‐methyl‐1,3‐dioxa‐2‐one) (PTMC‐MOE3OM) and copolymers, bearing oligo ethylene glycol (OEG) at the side chain of PTMC backbone, were selected to investigate the cloud point behavior by solvents such as PBS, water, 10% ethanol solution and various ionic strengths. A pH‐responsive copolymer, poly(TMCM‐MOE3OM‐co‐(5‐methyl‐5‐carboxylic‐1,3‐dioxane‐2‐one)) as carboxylic acid carbonate showed a decreased critical temperature at pH 2. Photo‐responsive copolymer, poly(TMCM‐MOE3OM‐co‐coumarin derivatives) bearing 1% and 10% of photo‐induced molecules (7‐[(5‐(5‐methyl‐1,3‐dioxa‐2‐one)methoxy)]‐methoxy coumarin (TMCM‐coumarin)) exhibited a low cloud point because of the hydrophobic moieties. Meanwhile, alternative coumarin polymer including 2% of 4‐methyl‐7‐[(5‐(5‐methyl‐1,3‐dioxa‐2‐one)methoxy)butoxy)]‐methoxy coumarin (TMCM‐4‐methyl‐coumarin) has been successfully synthesized and copolymerized as a novel molecule. The various combinations of monomers were studied and the significant properties were determined via external triggers after copolymerization. This study showed basically synthetic progress toward designs and trivial rationalization of thermoresponsive copolymers close to body temperature. At present, various pendant groups as side part affect to the lower critical solution temperature (LCST) and biodegradable polymer in order to utilize the actual external stimuli application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3466–3474     

Learning-based compressed sensing for infrared image super resolution

This paper presents an infrared image super-resolution method based on compressed sensing (CS). First, the reconstruction model under the CS framework is established and a Toeplitz matrix is selected as the sensing matrix. Compared with traditional learning-based methods, the proposed method uses a set of sub-dictionaries instead of two coupled dictionaries to recover high resolution (HR) images. And Toeplitz sensing matrix allows the proposed method time-efficient. Second, all training samples are divided into several feature spaces by using the proposed adaptive k-means classification method, which is more accurate than the standard k-means method. On the basis of this approach, a complex nonlinear mapping from the HR space to low resolution (LR) space can be converted into several compact linear mappings. Finally, the relationships between HR and LR image patches can be obtained by multi-sub-dictionaries and HR infrared images are reconstructed by the input LR images and multi-sub-dictionaries. The experimental results show that the proposed method is quantitatively and qualitatively more effective than other state-of-the-art methods.     

A Quick Color Test to Detect Lead Release From Glazed Ceramic and Enameled Metalware

Abstract

A color test is presented for the purpose of quickly identifying glazed ceramic and/or enameled metalware which releases excessive Pb. Citric acid solution on filter paper is used to extract Pb from the ware and a Pb-sensitive chromogen indicates the presence of Pb on the paper. The quick color test takes approximately 30 min and is useful for screening ware to determine the need for testing by the 24-h method of the Association of Official Analytical Chemists/American Society for Testing and Materials.     

Dual‐responsive supramolecular self‐assembly of inclusion complex of an azobenzene‐ended poly(ε‐caprolactone) with a water‐soluble pillar[6]arene and its application in controlled drug release

Dual photo‐ and pH‐responsive polymeric vesicles are constructed from a host–guest complex between a water‐soluble pillar[6]arene and an azobenzene ended functionalized poly(ε‐caprolactone). Reversible morphological transitions between vesicles and solid aggregates are achieved upon repeated UV stimulus and pH stimulus. Moreover, the polymeric vesicles present excellent cytocompatibility toward HepG2 cells and can be further applied for controlled release of a hydrophilic model drug, DOX?HCl. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2477–2482     

Solvent replacement to thermo‐responsive nanoparticles from long‐subchain hyperbranched PSt grafted with PNIPAM for encapsulation

Long‐subchain hyperbranched polystyrene (lsc‐hp PSt) with uniform subchain length was obtained through copper‐catalyzed azide‐alkyne cycloaddition click chemistry from seesaw macromonomer of PSt having one alkynyl group anchored at the chain centre and two azido group attached to both chain ends [alkynyl‐(PSt‐N₃)₂]. After precipitation fraction, different portions of lsc‐hp PSt having narrow overall molecular weight distribution were obtained for further grafting with alkynyl‐capped poly(N‐isopropylacrylamide) (alkynyl‐PNIPAM), which was obtained via single‐electron transfer living radical polymerization of NIPAM with propargyl 2‐bromoisobutyrate as the initiator and grafted onto the peripheral azido groups of lsc‐hp PSt via click chemistry. Thus, amphiphilic lsc‐hp PSt grafted with PNIPAM chains (lsc‐hp PSt‐g‐PNIPAM) was obtained and would have star‐like conformation in tetrahydrofuran (THF). By replacing THF with water, lsc‐hp PSt‐g‐PNIPAM was dissolved at molecular level in aqueous solution due to the hydrophilicity of PNIPAM and exhibited thermal induced shrinkage of PNIPAM arms. The water‐insoluble lsc‐hp PSt would collapse densely and could be served as a reservoir to absorb hydrophobic chemicals in aqueous solution. The influence of overall molecular weight of lsc‐hp PSt on the absorption of pyrene was studied. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Simultaneous quantification of atenolol and chlorthalidone in human plasma by ultra‐performance liquid chromatography–tandem mass spectrometry

A simple, sensitive and reproducible ultra‐performance liquid chromatography–tandem mass spectrometry method has been developed for the simultaneous determination of atenolol, a β‐adrenergic receptor‐blocker and chlorthalidone, a monosulfonamyl diuretic in human plasma, using atenolol‐d7 and chlorthalidone‐d4 as the internal standards (ISs). Following solid‐phase extraction on Phenomenex Strata‐X cartridges using 100 μL human plasma sample, the analytes and ISs were separated on an Acquity UPLC BEH C₁₈ (50 mm × 2.1 mm, 1.7 µm) column using a mobile phase consisting of 0.1% formic acid–acetonitrile (25:75, v/v). A tandem mass spectrometer equipped with electrospray ionization was used as a detector in the positive ionization mode for both analytes. The linear concentration range was established as 0.50–500 ng/mL for atenolol and 0.25–150 ng/mL for chlorthalidone. Extraction recoveries were within 95–103% and ion suppression/enhancement, expressed as IS‐normalized matrix factors, ranged from 0.95 to 1.06 for both the analytes. Intra‐batch and inter‐batch precision (CV) and accuracy values were 2.37–5.91 and 96.1–103.2%, respectively. Stability of analytes in plasma was evaluated under different conditions, such as bench‐top, freeze–thaw, dry and wet extract and long‐term. The developed method was superior to the existing methods for the simultaneous determination of atenolol and chlorthalidone in human plasma with respect to the sensitivity, chromatographic analysis time and plasma volume for processing. Further, it was successfully applied to support a bioequivalence study of 50 mg atenolol + 12.5 mg chlorthalidone in 28 healthy Indian subjects. Copyright © 2015 John Wiley & Sons, Ltd.     

Cyclic welding behavior of covalent adaptable network polymers

Surface welding effect of covalent adaptable network (CAN) polymers enables self‐healing, reprocessing and recycling of thermosets, but little is known about their welding behaviors during repeated welding‐peeling cycles. In this article, we study the cyclic welding effect of an epoxy based thermal‐sensitive CAN. Surface roughness is generated by rubbing the sample on sandpapers with different grid sizes. The welding‐peeling cycles are repeated on the same pair of samples for five times, with roughness amplitude and interfacial fracture energy measured in each cycle. It is shown that the roughness gradually decreases during the repeated welding cycles, especially when a long welding time or high welding pressure is applied. Even though lower roughness amplitude promotes the contact area, the interfacial fracture energy reduces due to the increased BER activation energy after long‐time heating. A multiscale constitutive model is adopted, where we incorporate an explicit expression of interfacial contact area as a function of root‐mean‐square roughness parameter. The model is able to capture the evolving interfacial fracture energy during repeated welding cycles by using the measured roughness parameter, network modulus and BER activation energy. The study provides theoretical basis for the design and applications of CANs involving cyclic welding‐peeling operations. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 402–413.     

Enhanced electron transfer by bovine serum albumin covalently attached to glassy carbon electrode and its application to determination of hydroquinone

Bovine serum albumin (BSA) was covalently attached to glassy carbon electrode (GCE) surface by the electrochemical method. An enhancement for the redox of hydroquinone (HQ) on BSA/GCE was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy measurement. The electron transfer rate constant (k _s) on the BSA/GCE electrode is almost three orders of magnitude higher than that on bare GCE. The enhancing effect can be attributed to the electrostatic force between the positively charged HQ and negatively charged BSA. It is found that the enhanced redox process of HQ can be used to determine HQ sensitively. The oxidation current can reach 95% of its steady-state value within 30 s. The linear range for HQ determination is from 2.5 × 10^?8 M to 1.325 × 10^?6 M with a detection limit of 8.6 × 10^?9 M at a signal-to-noise ratio of 3. The study may provide a simple, rapid and sensitive method for determination of HQ which is present in the natural environment and in chemical industry effluent.     

Thermoresponsive polymersome from a double hydrophilic block copolymer

The article describes synthesis and thermally triggered self‐assembly of a Poly (ethylene oxide)‐block‐poly (N‐insopropylacrylamide) (PEO‐b‐PNIPAm) in aqueous medium. At rt, the polymer remains as unimer, however, at lower critical solution temperature (LCST) of PNIPAm (32 °C), it forms a rather large undefined aggregate which at slightly elevated temperature (～40 °C) converges to well defined polymersome structure (Critical aggregation concentration = 0.45 mg/mL) with hydrodynamic diameter of 40–50 nm. By lowering the temperature, initial swelling of the compact vesicle followed by reversible disassembly to unimer was noticed. The polymersome exhibits encapsulation ability to a hydrophilic dye Calcein which can be spontaneously released by lowering the temperature below cloud point. Likewise a hydrophobic dye namely 8‐Anilino‐1‐naphthalenesulfonic acid (ANS) can also be encapsulated and released by thermal trigger. Detail photoluminescence studies reveal ANS dye can be used as a generalized probe molecule for detecting LCST of a thermoresponsive polymer by “fluorescence on” above LCST even by cursory observation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2444–2451     

Effects of graft length and density of well‐defined graft polymers on the thermoresponsive behavior and self‐assembly morphology

A series of well‐defined thermoresponsive graft polymers with different lengths and graft densities, poly(glycidyl methacrylate)‐graft‐poly(N‐isopropylacrylate) (PGMA‐g‐PNIPAM), were successfully prepared by combination of controlled/living free radical polymerization and click chemistry. Effects of grafting length and density on the thermoresponsive behavior, aggregating mean diameter, and self‐assembly morphology are systematically investigated. The thermosensitive characteristics of graft polymers in aqueous solution prove that the length and graft density had positive co‐relationship with the lower critical solution temperature value and mean diameter of micelles as well as the size distribution, while the effect of graft length of polymers is more significant than that of density. Transmission electron microscopy analysis shows that the conformations of PGMA₄₅‐g‐PNIPAM₂₀ and PGMA₄₅‐g‐PNIPAM₄₆ with longer length and bigger grafting density in aqueous solutions are spherical nanoparticles with the increasing trend of the diameters, while that of PGMA₄₅‐g‐PNIPAM_{(73, 50%)} shows a spherical‐like morphology, which indicates that the graft length and density have a significant effect on the mean diameter of micelle but not on the self‐assembly morphology. These results reveal that to obtain desired thermoresponsive behavior and self‐assembly morphology of functional polymers, it is essential to design and fabricate the structure of graft polymers with proper length and graft density. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2442–2453