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Mara K. Kuenen James A. Mullin Rachel A. Letteri 《Journal of polymer science. Part A, Polymer chemistry》2021,59(19):2212-2221
With a vast, synthetically accessible compositional space and highly tunable hydrolysis rates, poly(β-amino ester)s (PBAEs) are an attractive degradable polymer platform. Leveraging PBAEs in a wide range of applications hinges on the ability to program degradation, which, thus far, has been frustrated by multiple confounding phenomena contributing to the degradation of these charged polyesters. Basic conditions accelerate hydrolysis, yet reduce solubility, limiting water access to amines and esters. Further, the high buffering capacity of PBAEs can render buffers ineffective at controlling solution pH. To unify understanding of PBAE degradation and solution properties, this study examines PBAE hydrolysis as a function of pH and buffer concentration as well as polymer hydrophobicity. At low buffer concentrations, the PBAE amines and the acid produced during hydrolysis control solution pH. Meanwhile, at high buffer concentrations that afford relatively constant pH, hydrolysis rate increases with pH, despite the reduced PBAE solubility. Increasing the hydrophobic content of PBAEs eventually hinders the capacity of the polymer to accept protons from solution, limiting the pH increase and slowing hydrolysis. These studies showcase the role of buffering on the pH-dependent degradation and solution properties of PBAEs, providing guidance for programming degradation in applications ranging from drug delivery to thermosets. 相似文献
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Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities
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Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
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Rachel L. McSwain Alison R. Markowitz Kenneth R. Shull 《Journal of Polymer Science.Polymer Physics》2004,42(20):3809-3821
To develop a greater understanding of interfacial interactions between a semicrystalline polymer and a glassy polymer, adhesion tests were performed on very thin layers of poly(ethylene oxide) (PEO) sandwiched between two layers of poly(tetramethyl bisphenol A polycarbonate) (TMPC). The tests were designed to provide intimate contact between the surfaces while they were heated above the melting point of the PEO and cooled back to room temperature. A contact mechanics approach, based on the Johnson, Kendall, and Roberts theory, was used to determine values of the energy release rate describing the energetic driving force for crack propagation within the interfacial region. The ability to measure crack propagation at large values of the energy release rate was limited by rupture of the silicone elastomer that was used to provide a sufficiently compliant matrix for the adhesion experiment. By cycling the tensile stress at relatively low loading levels, we were able to measure fatigue crack propagation at values of the energy release rate that did not result in failure of the elastomer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3809–3821, 2004 相似文献
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R. Grac M. Pugnet J.H. Collet B. Lambert C. De Matos H. L'Haridon A. Le Corre J.O. White 《Superlattices and Microstructures》1997,22(4):505-509
We report new results on the diffraction properties of photoinduced gratings in InGaAs/InGaAsP MQW structures. The original feature of this device is that the QWs are enclosed in an asymmetric Fabry–Perot microcavity in order to increase the diffraction efficiency. We observe oscillations in the diffraction efficiency due to resonant effects in the microcavity. The experimental spectra are compared with theory. Diffraction efficiency at 1.55 μm attains a maximum value of 2.7% at a write beam fluence of 260 μ J cm−2, and then decreases at higher fluences. We explain this phenomenon by an absorption saturation at high excitation. 相似文献
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Frank H.G.M. Wijnands Charles G. Crookes Paul M. Charles Richard M. Ash Ian F. Lealman Michael J. Robertson Anthony E. Kelly Kevin A. Williams Aeneas B. Massara Richard V. Penty Ian H. White 《Optical and Quantum Electronics》2002,34(10):959-973
An anomalous modulation in the wavelength spectrum has been observed in lasers with spot-size converters. This intensity modulation is shown to be caused by beating between the fundamental lasing mode and radiation modes in the taper. This results in a periodic modulation in the net gain spectrum, which causes wavelength jumps between adjacent net gain maxima, and a drive current dependent spectral width that is expected to affect system performance. The amplitude of this spectral modulation is reduced significantly by either using an angled rear-facet which reflects the beating radiation modes away from the laser axis, or by using a nonlinear, adiabatic taper. 相似文献
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We have characterized multidielectric scaled SONOS nonvolatile memory structures with the quasi-static linear voltage ramp (LVR) technique and dynamic pulse measurements. We have formulated physically-based ERASE/WRITE and retention methods with deep level amphoteric traps which capture and emit carriers to the bands in the silicon nitride film. Amphoteric trap parameters are extracted by the LVR technique. ERASE/WRITE and retention amphoteric trap model simulations agree well with the experimental dynamic pulse measurements. Experimental scaled SONOS structures have been fabricated with tunnel oxide XOT=20 Å, nitride XN=30 Å and blocking oxide XOB=55 Å and demonstrated a static flatband shift of 3.6 V with ±5 V programming voltages. These structures may be used as the nonvolatile memory element in high density VLSI circuits. 相似文献