ABC-Type Triblock Copolyacrylamides via Copper-Mediated Reversible Deactivation Radical Polymerization

The aqueous Cu(0)-mediated reversible deactivation radical polymerization (RDRP) of triblock copolymers with two block sequences at 0.0 °C is reported herein. Well-defined triblock copolymers initiated from PHEAA or PDMA, containing (A) 2-hydroxyethyl acrylamide (HEAA), (B) N-isopropylacrylamide (NIPAM) and (C) N, N-dimethylacrylamide (DMA), were synthesized. The ultrafast one-pot synthesis of sequence-controlled triblock copolymers via iterative sequential monomer addition after full conversion, without any purification steps throughout the monomer additions, was performed. The narrow dispersities of the triblock copolymers proved the high degree of end-group fidelity of the starting macroinitiator and the absence of any significant undesirable side reactions. Controlled chain length and extremely narrow molecular weight distributions (dispersity ~ 1.10) were achieved, and quantitative conversion was attained in as little as 52 min. The full disproportionation of CuBr in the presence of Me6TREN in water prior to both monomer and initiator addition was crucially exploited to produce a well-defined ABC-type triblock copolymer. In addition, the undesirable side reaction that could influence the living nature of the system was investigated. The ability to incorporate several functional monomers without affecting the living nature of the polymerization proves the versatility of this approach.

The Durability of Zirconia/Resin Composite Shear Bond Strength using Different Functional Monomer of Universal Adhesives

Objective This study examined the effectiveness of different functional monomers in universal adhesives on zirconia/resin composite bond strength both before and after thermocycling. Four universal adhesives (G-premio bond universal, GPU; Clearfil Tri-S bond universal, CTB; Optibond Universal, OBU; Tetric N-bond universal; TNU), one adhesive (single bond 2; SB2), and one ceramic primer (Clearfil ceramic primer plus, CCP) were used in this study. Materials and Methods Zirconia discs were prepared and embedded in acrylic. Specimens were polished and sandblasted with alumina. The specimens were randomly divided into two groups (24 hours and the thermocycled), and each group was divided into six subgroups (n = 10), according to zirconia surfaces treatments: no Tx, CCP + SB2, GPU, CTB, OBU, TNU. An Ultradent mold was located on top of the treated zirconia surface. The resin composite was filled into the mold and then light-cured. A universal testing device was used to determine the shear bond strength. Statistical Analysis The data were statistically analyzed using one-way ANOVA and Tukey's test. Results After water storage for 24 hours, the shear bond strengths were GPU > CCP + SB2 = CTB = OBU = TNU > no Tx (p < 0.05). After thermocycling, the shear bond strengths were CCP + SB2 = GPU = CTB = TNU > OBU > no Tx (p < 0.05). Conclusion The universal adhesives containing 10-MDP exhibited the best performance in the shear bond strength of the zirconia/resin composite interface both before and after thermocycling.

Rapid Detection of Dimethoate in Soybean Samples by Microfluidic Paper Chips Based on Oil-Soluble CdSe Quantum Dots

Given the imperative of monitoring organophosphorus pesticides (OPs) residues in the ecosystem, here a novel, facile and sensitive fluorescence sensor is presented for the rapid detection of dimethoate. In this work, surface molecularly imprinted polymer (SMIP) and microfluidic technology had been introduced to enhance the selectivity and portability of the described methodology. Oil-soluble CdSe quantum dots (QDs) synthesized in a green way were used as fluorescent material for the selective detection of dimethoate on the basis of static quenching and photoinduced electron transfer mechanism. Among many kinds of paper materials, glass fiber paper was used as the novel substrate of paper chip due to low pristine fluorescence and better performance when combining CdSe QDs. In the process of molecular imprinting, the interaction between several functional monomers and dimethoate molecule was investigated and simulated theoretically by software to improve the selectivity of the sensor. Consequently, the fabricated novel detection platform could effectively respond to dimethoate in 10 min with the concentration range of 0.45–80 μmol/L and detection limit of 0.13 μmol/L. The recovery in the spiked experiment soybean sample was in an acceptable range (97.6–104.1%) and the accuracy was verified by gas chromatography-mass spectrometry, which signified the feasibility and potential in food sampling.

Methacryloyl-GlcNAc Derivatives Copolymerized with Dimethacrylamide as a Novel Antibacterial and Biocompatible Coating

Improving medical implants with functional polymer coatings is an effective way to further improve the level of medical care. Antibacterial and biofilm-preventing properties are particularly desirable in the area of wound healing, since there is a generally high risk of infection, often with a chronic course in the case of biofilm formation. To prevent this we here report a polymeric design of polymer-bound N-acetyl-glucosamine-oligoethylene glycol residues that mimic a cationic, antibacterial, and biocompatible chitosan surface. The combination of easy to use, crosslinkable, thin, potentially 3D-printable polymethacrylate layering with antibacterial and biocompatible functional components will be particularly advantageous in the medical field to support a wide range of implants as well as wound dressings. Different polymers containing a N-acetylglucosamine-methacryloyl residue with oligoethylene glycol linkers and a methacryloyl benzophenone crosslinker were synthesized by free radical polymerization. The functional monomers and corresponding polymers were characterized by 1H, 13C NMR, and infrared (IR) spectroscopy. The polymers showed no cytotoxic or antiadhesive effects on fibroblasts as demonstrated by extract and direct contact cell culture methods. Biofilm formation was reduced by up to 70% and antibacterial growth by 1.2 log, particularly for the 5% GlcNAc-4EG polymer, as observed for Escherichia coli and Staphylococcus aureus as clinically relevant Gram-negative and Gram-positive model pathogens.

Binding of the kringle-2 domain of human plasminogen to streptococcal PAM-type M-protein causes dissociation of PAM dimers

M-protein (PAM) largely contributes to the pathogenesis of Pattern D Group A Streptococcus pyogenes (GAS). However, the mechanism of complex formation is unknown. In a system consisting of a Class II PAM from Pattern D GAS isolate NS88.2 (PAMNS88.2), with one K2hPg binding a-repeat in its A-domain, we employed biophysical techniques to analyze the mechanism of the K2hPg/PAMNS88.2 interaction. We show that apo-PAMNS88.2 is a coiled-coil homodimer (M.Wt. ~80 kDa) at 4°C - 25°C, and is monomeric (M.Wt. ~40 kDa) at 37°C, demonstrating a temperature-dependent dissociation of PAMNS88.2 over a narrow temperature range. PAMNS88.2 displayed a single tight binding site for K2hPg at 4°C, which progressively increased at 25°C through 37°C. We isolated the K2hPg/PAMNS88.2 complexes at 4°C, 25°C, and 37°C and found molecular weights of ~50 kDa at each temperature, corresponding to a 1:1 (m:m) K2hPg/PAMNS88.2 monomer complex. hPg activation experiments by streptokinase demonstrated that the hPg/PAMNS88.2 monomer complexes are fully functional. The data show that PAM dimers dissociate into functional monomers at physiological temperatures or when presented with the active hPg module (K2hPg) showing that PAM is a functional monomer at 37°C.

Influence of Pre-Etched Area and Functional Monomers on the Enamel Bond Strength of Orthodontic Adhesive Pastes

This study was performed to investigate the influence of pre-etching area and functional monomers in orthodontic adhesive pastes on enamel bond strength. Bovine enamel was partially pre-etched with phosphoric acid for 30 s over areas with a diameter of 1.0, 2.0 or 3.0 mm, and metal brackets were then bonded with or without functional monomers in the orthodontic adhesive paste. For the baseline groups, the whole adherent area was pre-etched. The shear bond strength (SBS) and adhesive remnant index (ARI) were determined. The adhesive paste/enamel interfaces were observed by scanning electron microscopy (SEM). Although the adhesive paste with functional monomers showed higher SBS than the functional monomer-free adhesive paste in all groups, there were no significant differences in SBS between them regardless of the pre-etched area. The SBS increased with increasing pre-etched area in both orthodontic adhesive pastes. In SEM images of adhesive paste/enamel interfaces, although adhesive with functional monomers showed excellent adaptation, the functional monomer-free adhesive paste showed gap formation at the interface. These findings suggested that the pre-etching area greatly influenced bond strength, regardless of the presence or absence of the functional monomer in the orthodontic adhesive paste.

Organic Solvent Sensors Using Polymer-Dispersed Liquid Crystal Films with a Pillar Pattern

An organic solvent sensor of polymer-dispersed liquid crystals (PDLCs) film is fabricated by a combination of tri-functional monomers and LCs. When the patterned PDLC film comes into contact with the organic solvent, the organic solvent will penetrate into the film to induce the orientation of the liquid crystals, which will change from an ordered to a disordered state, which causes the PDLC film to scatter incident light. The experiment used acetone and ethanol as the organic solvents of interest. The results show that the patterned PDLC film has a stronger response to acetone than to ethanol. Based on the difference in the intensity of light scattering and the response time of the patterned PDLC film to different organic solvents, the results can be used to identify and recognize different types of organic solvents.

Synergetic Effect of Dual Functional Monomers in Molecularly Imprinted Polymer Preparation for Selective Solid Phase Extraction of Ciprofloxacin

Background: Ciprofloxacin (CIP), an important broad-spectrum fluoroquinolone antibiotic, was often used as a template molecule for the preparation of imprinted materials. In this study, methacrylic acid and 2-vinylpyridine were employed for the first time as dual functional monomers for synthesizing ciprofloxacin imprinted polymers. Methods: The chemical and physicochemical properties of synthesized polymers were characterized using Fourier transform-infrared spectroscopy, thermogravimetric analysis-differential scanning calorimetry, scanning electron microscopy, and nitrogen adsorption-desorption isotherm. The adsorption properties of ciprofloxacin onto synthesized polymers were determined by batch experiments. The extraction performances were studied using the solid phase extraction and HPCL-UV method. Results: The molecularly imprinted polymer synthesized with dual functional monomers showed a higher adsorption capacity and selectivity toward the template molecule. The adsorbed amounts of ciprofloxacin onto the imprinted and non-imprinted polymer were 2.40 and 1.45 mg g−1, respectively. Furthermore, the imprinted polymers were employed as a selective adsorbent for the solid phase extraction of ciprofloxacin in aqueous solutions with the recovery of 105% and relative standard deviation of 7.9%. This work provides an alternative approach for designing a new adsorbent with high adsorption capacity and good extraction performance for highly polar template molecules.