Nanoscale surface morphology and monomer concentration dependence on impedance of electrocoated 2,2-dimethyl-3,4-propylene-dioxythiophene on carbon fiber microelectrode

Poly(2,2-Dimethyl-3,4-propylenedioxythiophene) (PProDOT-Me2) thin films have been cyclovoltametrically coated onto carbon fiber microelectrode (CFME) as an active functionalized microelectrode. An electrochemical impedance spectroscopic study on the prepared electrodes is reported in this paper which electropolymerization performed under different initial monomer concentrations. The electrochemical impedance data fitted to equivalent circuit model, used to find out numerical values of the proposed components. Effect of the parameters on the capacitive behavior of the (PProDOT-Me2) coated carbon fiber microelectrode and morphology of films obtained by AFM and SEM was discussed. Highly porous coating was obtained at 100 mV/s scan rate and 10 cycles. EDX and ATR-FTIR results indicated the doping of anion of electrolyte due to formation of polaronic and bipolaronic sites. The presence of surface functional groups were determined by ATR-FTIR. Nanoscale conjugated polymer modified carbon fiber microelectrodes exhibited high capacitance of approximately 90 degrees phase angle, and vertical line in Nyquist plot. The capacitive behavior of CFME was increased by this very thin film coating of PProDOT-Me2. The electroactivity of Poly 2,2-Dimethyl-3,4-propylenedioxythiophene on the carbon fiber microelectrode open the possibility of using these coated electrodes for electrochemical microsupercapacitors and biosensor electrodes.     

Experimental characterization of the impact‐damage tolerance of a cross‐ply graphite‐fiber/epoxy laminate

In this study, the impact‐damage tolerance of a graphite‐fiber/epoxy composite laminate is studied by examining the correlation between the impact force and the resulting delamination area in the laminate. The cross‐ply [0₂/90₂/0₂]_s composite laminate was made of thermosetting P7051S‐20Q‐1000 prepregs (Toray Composites America). A Hopkinson pressure bar (HPB) was employed to create the impulsive loading with varying magnitude. Transient impact force, displacement, impact power, and transmitted impact energy were calculated using the transient signals recorded from the strain gage mounted on the HPB. Impulsive loads with controllable magnitude were used to induce delamination damage with varying size in the composite samples. Nondestructive evaluation based on a novel ultrasonic pulse‐echo reflector technique was used successfully for characterizing the delamination areas in the thin composite samples with thickness ∼2 mm. The present experimental results indicate that there exists a very good linear correlation between the impact force (e.g. the peak force, impact impulse, peak impact power, and the transmitted impact energy of the first impact force pulse exerted by the HPB) and the delamination area of the composite samples. This correlation can be used to determine the threshold of the impact force that initiates the delamination damage in the composite laminate. In contrast to the weight‐drop test, the present experimental method successfully examined the impact damage tolerance of polymer matrix composites (PMCs) subjected to impulsive loading with very high force magnitude and ultra short duration such as the typical ballistic impact. The present method and results can be used for the study of impact damage tolerance of PMCs with varying lay‐ups and interface modifications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Nano-engineering of high-performance PA6.6 nanocomposites by the integration of CVD-grown carbon fiber on graphene as a bicomponent reinforcement by melt-compounding

In this study, long carbon nanofibers (CNFs) were grown on graphene nanoplatelets (GNPs) by chemical vapor deposition (CVD) technique to develop three-dimensional (3D) bicomponent nanostructures. The structure and properties of graphene before and after CVD process were investigated in details. X-ray photoelectron analysis depicted the formation of Fe-C bonds by the deposition of carbon atoms on the catalyst surface of Fe₂O₃. This hybrid additive was firstly used as a reinforcing agent in melt compounding to fabricate PA6.6-based nanocomposites with enhanced mechanical and thermal properties. Both GNP and CNF-GNP have enough surface oxygen functional groups to improve the interfacial interactions with polyamide matrix and thus provide good wettability. Also, both neat GNP and its bicomponent additive with CNF also acted as a nucleating agent and allowed the crystal growth in nanocomposite structure. Homogeneous dispersion of nanoparticles was achieved by using thermokinetic mixer during compounding by applying high shear rates. Mechanical results showed that 23 and 34% improvement in flexural and tensile modulus values, respectively, was attained by the addition of 0.5 wt % CNF-GNP hybrid additive. The heat distortion temperature and Vicat softening temperature of the resulting PA6.6 nanocomposites were improved compared to neat PA6.6 material indicating performance enhancement at higher service temperature conditions. CNF was successfully grown on Fe-loaded GNP by CVD method and this hybrid additive was compounded with PA6.6 by melt-mixing process. Mechanical results showed that 34% improvement in tensile modulus value was attained by the addition of 0.5 wt % CNF-GNP hybrid additive because it acted as a nucleating agent and allowed the crystal growth in the nanocomposite structure. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48347.     

Effect of initiators and ethoxylation degree of non‐ionic emulsifiers on vinyl acetate and butyl acrylate emulsion copolymerization in the loop reactor

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate and potassium persulfate initiators, mixture of non‐ionic and anionic emulsifiers, and polyvinyl alcohol as protective colloid in a loop reactor. The monomer ratio was chosen 85:15. The series of non‐ionic emulsifiers, which have 10–40 moles ethoxylated nonyl phenol, were combined with Nansa 66 (sodium dodecyl benzene sulfonate). The effects of the initiators on the physicochemical properties of copolymers were investigated by measuring conversion, viscosity, molecular weight, molecular weight distribution, and surface tension, respectively by using gravimetric method, Brookfield viscometer, gel permeation chromatograpy (GPC), and ring method. The effects of ethoxylation degrees of the non‐ionic emulsifiers to the same properties of copolymers were also investigated. It was determined that the copolymer viscosities showed different tendency for two initiators. They were increased by the increasing ethoxylation degree of the non‐ionic emulsifier for ammonium persulfate. In contrast, latex viscosity was decreased by increasing the ethoxylation degree in presence of potassium persulfate. Similar changes were also found in number average molecular weights of copolymers. On the other hand, weight average molecular weights of copolymers increased by increasing the ethoxylation degree of the non‐ionic emulsifier for both initiators. In the case of potassium persulfate, the surface tension values of copolymers increased by increasing the ethoxylation degree, but generally increasing the ethoxylation degree did not affect the surface tension of copolymer very seriously for two initiators. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 537–543, 2003     

Electrochemical composite formation of thiophene and N-methylpyrrole polymers on carbon fiber microelectrodes: Morphology,characterization by surface spectroscopy,and electrochemical impedance spectroscopy

Electrochemical composite thin film formation (∼0.6–0.7 μm) of thiophene and N-methylpyrrole on carbon fiber microelectrodes (diameter ∼7 μm) was carried out by cyclic voltammetry in order to understand and improve the surface properties and capacitance behaviour of carbon fibers. Carbon fiber microelectrodes were coated with polythiophene and N-methylpyrrole was electrografted onto the thiophene electrode. The electrocoated carbon fiber surface mophology was characterized by scanning electron microscopy and atomic force microscopy and by FTIR-reflectance spectroscopy for their composition. The effect of monomer concentration and scan number on electropolymerization has also been investigated. The impedance behaviour of composite electrodes was characterized by electrochemical impedance spectroscopy. The composite of polythiophene and poly-N-methylpyrrole exhibits better charge storage properties than polythiophene coated carbon fiber microelectrodes.     

Syk- and Lyn-dependent phosphorylation of Syk on multiple tyrosines following B cell activation includes a site that negatively regulates signaling

The Syk protein tyrosine kinase is an essential component of the B cell Ag receptor signaling pathway. Syk is phosphorylated on tyrosine following B cell activation. However, the sites that are modified and the kinases responsible for these modifications have yet to be determined. To approach this problem, we used a mapping strategy based on the electrophoretic separation of peptides on alkaline polyacrylamide gels to identify the tryptic phosphopeptides derived from metabolically labeled Syk. In this work, we report that Syk from activated B cells is phosphorylated principally on six tyrosines: one located between the tandem SH2 domains (Tyr130); three in the linker region (Tyr317, Tyr342, and Tyr346); and two in the catalytic domain (Tyr519 and Tyr520). The linker region sites are the primary targets of the Src family protein tyrosine kinase, Lyn, and include a site that negatively (Tyr317) regulates receptor signaling. Efficient phosphorylation of the catalytic domain and inter-SH2 domain tyrosines is catalyzed primarily by Syk itself, but only occurs to an appreciable extent in cells that express Lyn. We propose that these sites are phosphorylated following the binding of Syk to immunoreceptor tyrosine-based activation motif.     

Virtual Pharmacophore Screening Identifies Small-Molecule Inhibitors of the Rev1-CT/RIR Protein–Protein Interaction

Translesion synthesis (TLS) has emerged as a mechanism through which several forms of cancer develop acquired resistance to first-line genotoxic chemotherapies by allowing replication to continue in the presence of damaged DNA. Small molecules that inhibit TLS hold promise as a novel class of anticancer agents that can serve to enhance the efficacy of these front-line therapies. We previously used a structure-based rational design approach to identify the phenazopyridine scaffold as an inhibitor of TLS that functions by disrupting the protein–protein interaction (PPI) between the C-terminal domain of the TLS DNA polymerase Rev1 (Rev1-CT) and the Rev1 interacting regions (RIR) of other TLS DNA polymerases. To continue the identification of small molecules that disrupt the Rev1-CT/RIR PPI, we generated a pharmacophore model based on the phenazopyridine scaffold and used it in a structure-based virtual screen. In vitro analysis of promising hits identified several new chemotypes with the ability to disrupt this key TLS PPI. In addition, several of these compounds were found to enhance the efficacy of cisplatin in cultured cells, highlighting their anti-TLS potential.     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

Synthesis and characterization of mid-chain macrophotoinitiator of poly(ε-caprolactone) by combination of ROP and click chemistry

Well-defined mid-chain functional macrophotoinitiator of poly(ε-caprolactone) (PCL-PI-PCL) was synthesized by combination of ring-opening polymerization (ROP) and click chemistry strategy. Dibromo functional photoinitiator (Br–PI–Br) was prepared by the condensation of 2-bromopropanoyl bromide with 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl propan-1-one (PI). Subsequently, terminal bromo groups in Br–PI–Br were converted to azido groups to form diazido functional photoinitiator (N₃–PI–N₃) using NaN₃. Well-defined precursor alkyne-functionalized PCL (alkyne-PCL) was prepared by ROP of ε-CL in the presence of propargyl alcohol as the initiator and stannous-2-ethylhexanoate (Sn(Oct)2) as the catalyst. Finally, the alkyne-functionalized PCL was coupled with N₃–PI–N₃ with high efficiency by click chemistry. The spectroscopic studies showed that low-polydispersity PCL with desired photoinitiator functionality in the middle of the chain was obtained.     

Palmtree: An IP alias resolution algorithm with linear probing complexity

Internet topology mapping studies utilize large scale topology maps to analyze various characteristics of the Internet. IP alias resolution, the task of mapping IP addresses to their corresponding routers, is an important task in building such topology maps. In this paper, we present a new probe-based IP alias resolution tool called palmtree. Palmtree can be used to complement the existing schemes in improving the overall success of alias resolution process during topology map construction. In addition, palmtree incurs a linear probing overhead to identify IP aliases. The experimental results obtained over Internet2 and GEANT networks as well as four major Internet Service Providers (ISPs) present quite promising results on the utility of palmtree in obtaining more accurate network topology maps.