A novel polymer‐based genosensor for the detection and quantification of Streptococcus pneumoniae in genomic DNA sample

The Streptococcus pneumoniae detection plays an important role in the diagnosis and monitoring of pneumococcal diseases. A genosensor based on graphite electrodes modified with polymer was developed for such detection. First, the poly(4‐aminophenol) film was electrochemically deposited on a graphite electrode. Afterward, an S. pneumoniae‐specific oligonucleotide (Strep1), isolated from conserved regions of the bacterial genome, was immobilized onto the modified electrode surface and used for the test with complementary target oligonucleotide (Strep2) or genomic DNA. The genosensor was evaluated using electrochemical techniques and atomic force microscopy. Poly(4‐aminophenol) film caused an increase in probe immobilization, monitoring the guanine oxidation peak. The detection limits obtained using differential pulse voltammetry and electrochemical spectroscopy impedance were 54 and 28 ng mL^?1, respectively. The novel genosensor was efficient for the immobilization and detection of S. pneumoniae genomic DNA. POLYM. ENG. SCI., 58:1308–1314, 2018. © 2017 Society of Plastics Engineers     

The effect of different cementing strategies and adhesive interface aging on microtensile bond strength (μTBS) of lithium disilicate ceramics to dentin

This study evaluated the effect of different cementing strategies and adhesive interface aging on microtensile bond strength (μTBS) of lithium disilicate ceramic (IPS e.max CAD) to dentin. Forty coronal dentin fragments were randomly assigned to four groups according to the cementing strategy used to bond lithium disilicate ceramic to coronal dentin surface (n = 10): U200 (self-adhesive resin cement (RC) RelyX U200®/3 M ESPE), SBU (single-step self-etching adhesive system (AS) Single Bond Universal®/3 M ESPE + RelyX ARC®/3 M ESPE RC), AdperSB (two-step etch-and-rinse AS Single Bond 2®/3 M + RelyX ARC®/3 M ESPE RC) and Scotchbond (three-step etch-and-rinse AS Scotchbond Multi-Purpose®/3 M + RelyX ARC®/3 M RC). After 48 h, the ceramic-tooth blocks were sectioned perpendicular to the adhesive interface in the form of sticks and randomly subdivided into two groups according to when they were to be submitted to μTBS testing: immediately or 6 months after storage in water. Some sticks were kept for analysis of the adhesive interface by scanning electron microscopy (SEM). The μTBS test was performed in a universal testing machine (0.5 mm/min). The data (MPa) were analyzed using split-plot ANOVA and Tukey’s test (α = 0.05). Water storage decreased μTBS in all cementing strategies. The μTBS was greatest in the Scotchbond group and lowest in the U200 group, at both storage times. No signs of interface degradation were detected under SEM after water storage. In conclusion, water storage decreased bond strength, regardless of the adhesive cementation strategy, and that the three-step adhesive system/dual-cure resin cement ultimately performed better in terms of bond strength.     

Self‐aggregated nanoparticles of N‐dodecyl,N′‐glycidyl(chitosan) as pH‐responsive drug delivery systems for quercetin

In this study, pH‐responsive amphiphilic chitosan (CS) nanoparticles were used to encapsulate quercetin (QCT) for sustained release in cancer therapy. The novel CS derivatives were obtained by synthesis with 2,3‐epoxy‐1‐propanol, also known as glycidol, followed by acylation with dodecyl aldehyde. Characterization was performed by spectroscopic, viscosimetric, and size‐determination methods. Critical aggregation concentration, morphology, entrapment efficiency, drug release profile, cytotoxicity, and hemocompatibility studies were also carried out. The average size distribution of the self‐assembling nanoparticles measured by dynamic light scattering ranged from 140 to 300 nm. In vitro QCT release and Korsmeyer–Peppas model indicated that pH had a major role in drug release. Cytotoxicity assessments indicated that the nanoparticles were non‐cytotoxic. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay further revealed that QCT‐loaded nanoparticles could inhibit MCF‐7 cell growth. In vitro erythrocyte‐induced hemolysis indicated the good hemocompatibility of the nanoparticles. These results suggest that the synthesized copolymers might be potential carriers for hydrophobic drugs in cancer therapy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45678.     

A new thermoset for separation of polystyrene and naphthalene in preparative chromatography

Many research groups in recent years have demonstrated the importance of obtaining new materials and reducing environmental impact. In this context, the chemical modification of cellulose and its derivatives has received much attention. This study synthesized cellulose acetate gel (CAMDIH) obtained through the modification of cellulose acetate (CA) with a degree of substitution of 2.5, by crosslinking reactions using 4,4′‐diphenylmethane diisocyanate in homogeneous medium. The formation of crosslinks were observed by the presence of Fourier transform infrared spectroscopy absorption bands at 3046 and 864 cm^?1, which correspond to the absorption of aromatic groups associated with the incorporation of 4,4′‐diphenylmethane diisocyanate in the CA structure. The potential applications of the gel as a stationary phase were tested using column chromatography in the fractionation and separation of standard solutions of polystyrene and naphthalene. The findings showed the effectiveness of the gel as a stationary state in the separation of mixture compounds. Furthermore, the study found that CAMDHI is an innovative material when considering its simple synthesis and the low costs involved in the process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46063.     

Synthesis and Characterization of Allyl Fatty Acid Derivatives as Reactive Coalescing Agents for Latexes

This work evaluated the use of allyl fatty acid esters derived from vegetable oil (palmitic acid, soybean and sunflower oils) as reactive coalescing agents in a waterborne latex system. Allyl fatty acid derivatives (AFAD) from vegetable oils were synthesized by two different processes. The synthesis was monitored by IR-spectroscopy and the final product characterized by FT-IR, GC–MS, ¹H and ¹³C NMR. The presence of conjugated double bonds in the aliphatic chain was confirmed, which is a determinant for the proposed autoxidative latexes drying mechanism. Each of the AFAD were subsequently added to a standard acrylic emulsion, in order to study its potential as reactive coalescing agent. The minimum film-forming temperature (MFT), glass transition temperature (T _g), drying time and rubbing resistance to solvents were evaluated. The results showed that, when added to water-borne acrylic resins, an AFAD acts as a non-volatile plasticizer capable of autoxidative crosslinking with itself.     

Cold Crystallization of PLLA Studied by Simultaneous SAXS and WAXS

Summary: The cold crystallization process of initially amorphous poly(L ‐lactic acid), PLLA, with two different molecular weights, during a heating at 2 °C/min, was investigated by DSC and time‐resolved simultaneous SAXS and WAXS, using synchrotron radiation. Equatorial scans of the isotropic 2D‐SAXS patterns showed that the average Bragg long period (L_B) of PLLA samples was approximately constant with the development of cold crystallization up to a temperature that corresponded to a melt/re‐crystallization process that took place before the nominal melting peak seen by DSC. L_B values were found to be higher for the high molecular weight material. This was in accordance with the higher melting temperature observed in the high molecular weight PLLA that implied the existence of thicker lamellae. WAXS results showed that the molecular weight did not apparently affect the crystal form and the final degree of crystallinity of PLLA. The Avrami parameters from WAXS and DSC were consistent, showing that the non‐isothermal cold crystallization of the two PLLA samples corresponded mainly to a three‐dimensional growth, although an imperfect crystallization process was involved at early times. The crystallization rate of PLLA, observed both by WAXS and DSC, decreased with increasing molecular weight.

SAXS profiles of PLLA2 as a function of temperature. The inset shows the 2D‐SAXS pattern obtained at 180 °C.     

Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

SiC whisker reinforced multi-carbides composites prepared from B4C and pyrolyzed rice husks via reactive infiltration

SiC whisker reinfored carbide-based composites were fabricated by a reactive infiltration method by using Si as the infiltrate. Rice husks (RHs) were pyrolyzed to SiC whiskers, particles and amorphous carbon, and were then mixed with different contents of B₄C as well as Mo powders. The mixtures were molded to porous preforms for the infiltration. The SiC whiskers and particles in the preform remained in the composite. Molten Si reacted with the amorphous carbon, B₄C as well as Mo in the preform during the infiltration, forming newly SiC, B₁₂(C,Si,B)₃ as well as MoSi₂. The upper values of elastic modulus, hardness and fracture toughness of the composites are 297.8 GPa, 16.8 ± 0.8 GPa, and 3.8 ± 0.2 MPa m^1/2, respectively. The influence of the phase composition of the composites on the mechanical properties and the fracture mechanism are discussed.     

A Synthetic MUC1 Glycopeptide Bearing βGalNAc‐Thr as a Tn Antigen Isomer Induces the Production of Antibodies against Tumor Cells

This study presents the synthesis of the novel protected O‐glycosylated amino acid derivatives 1 and 2 , containing βGalNAc‐SerOBn and βGalNAc‐ThrOBn units, respectively, as mimetics of the natural Tn antigen (αGalNAc‐Ser/Thr), along with the solid‐phase assembly of the glycopeptides NHAcSer‐Ala‐Pro‐Asp‐Thr[αGalNAc]‐Arg‐Pro‐Ala‐Pro‐Gly‐BSA ( 3 ‐BSA) and NHAcSer‐Ala‐Pro‐Asp‐Thr[βGalNAc]‐Arg‐Pro‐Ala‐Pro‐Gly‐BSA ( 4 ‐BSA), bearing αGalNAc‐Thr or βGalNAc‐Thr units, respectively, as mimetics of MUC1 tumor mucin glycoproteins. According to ELISA tests, immunizations of mice with βGalNAc‐glycopeptide 4 ‐BSA induced higher sera titers (1:320 000) than immunizations with αGalNAc‐glycopeptide 3 ‐BSA (1:40 000). Likewise, flow cytometry assays showed higher capacity of the obtained anti‐glycopeptide 4 ‐BSA antibodies to recognize MCF‐7 tumor cells. Cross‐recognition between immunopurified anti‐βGalNAc antibodies and αGalNAc‐glycopeptide and vice versa was also verified. Lastly, molecular dynamics simulations and surface plasmon resonance (SPR) showed that βGalNAc‐glycopeptide 4 can interact with a model antitumor monoclonal antibody (SM3). Taken together, these data highlight the improved immunogenicity of the unnatural glycopeptide 4 ‐BSA, bearing βGalNAc‐Thr as Tn antigen isomer.