Suzuki–Miyaura Cross‐Coupling of Unprotected Halopurine Nucleosides in Water—Influence of Catalyst and Cosolvent

Abstract

Reaction conditions for the Suzuki–Miyaura cross‐coupling of unprotected halopurine nucleosides with arylboronic acids in aqueous media were investigated. A series of arylated purine nucleosides was prepared in water without an organic cosolvent, using either Pd(PPh₃)₄ or Pd(OAc)₂/TPPTS as the catalyst.     

Microparticle ratiometric oxygen sensors utilizing near-infrared emitting quantum dots

Luminescent sensors incorporating two luminophores, an indicator and a reference, offer many advantages over intensity measurements from sensors made with one indicator dye. Quantum dots have yet to be widely employed as insensitive reference luminophores in such systems. This work describes the use of near-infrared emitting quantum dots in conjunction with a long-lifetime platinum(II) porphyrin phosphor in a microsphere-based, ratiometric oxygen sensor. The process for self-assembly of the nanocomposite system was developed, and the response and photostability of the prototypes were investigated. Results indicate the sensors possess excellent sensitivity (K(SV) = 0.00826 μM(-1)) at oxygen concentrations below 300 μM and were resistant to photobleaching. The sensor luminophores displayed minimal spectral overlap and little interference from excitation light, preventing the need for optical filters. A reversible photoenhancement of the quantum dot signal was also observed when exposed for extended periods of time. This work demonstrates the advantages of incorporating long-wavelength quantum dots into ratiometric intensity sensing schemes and highlights some key limitations that must be considered in their use.     

Technical efficiency estimation with multiple inputs and multiple outputs using regression analysis

Regression and linear programming provide the basis for popular techniques for estimating technical efficiency. Regression-based approaches are typically parametric and can be both deterministic or stochastic where the later allows for measurement error. In contrast, linear programming models are nonparametric and allow multiple inputs and outputs. The purported disadvantage of the regression-based models is the inability to allow multiple outputs without additional data on input prices. In this paper, deterministic cross-sectional and stochastic panel data regression models that allow multiple inputs and outputs are developed. Notably, technical efficiency can be estimated using regression models characterized by multiple input, multiple output environments without input price data. We provide multiple examples including a Monte Carlo analysis.     

35 J broadband femtosecond optical parametric chirped pulse amplification system

We report on what is believed to be the first large-aperture and high-energy optical parametric chirped pulse amplification system. The system, based on a three-stage amplifier, shows 25% pump-to-signal conversion efficiency and amplification of the full 70 nm width of the seed spectrum. Pulse compression to 84 fs achieved after amplification indicates a potential of 300 TW pulse power for 35 J amplified pulse energy.     

Self‐Assembling Peptide Gels for 3D Prostate Cancer Spheroid Culture

Progress in prostate cancer research is presently limited by a shortage of reliable in vitro model systems. The authors describe a novel self‐assembling peptide, bQ13, which forms nanofibers and gels useful for the 3D culture of prostate cancer spheroids, with improved cytocompatibility compared to related fibrillizing peptides. The mechanical properties of bQ13 gels can be controlled by adjusting peptide concentration, with storage moduli ranging between 1 and 10 kPa. bQ13's ability to remain soluble at mildly basic pH considerably improved the viability of encapsulated cells compared to other self‐assembling nanofiber‐forming peptides. LNCaP cells formed spheroids in bQ13 gels with similar morphologies and sizes to those formed in Matrigel or RADA16‐I. Moreover, prostate‐specific antigen (PSA) is produced by LNCaP cells in all matrices, and PSA production is more responsive to enzalutamide treatment in bQ13 gels than in other fibrillized peptide gels. bQ13 represents an attractive platform for further tailoring within 3D cell culture systems.     

Optical parametric chirped-pulse amplification source suitable for seeding high-energy systems

A short-pulse source based on optical parametric chirped-pulse amplification (OPCPA) technology has been developed with properties that make it a suitable seed for a high-energy OPCPA system. This source generated a diffraction-limited pulse at 910 nm with a full bandwidth of > 165 nm and a spectrum having a transform-limited pulse duration of less than 15 fs. The technique has potential for generating bandwidths > 200 nm and pulse durations < 10 fs.     

γ‐Irradiation of ultrahigh‐molecular‐weight polyethylene: Electron paramagnetic resonance and nuclear magnetic resonance spectroscopy and imaging studies of the mechanism of subsurface oxidation

The shelf aging of irradiated ultrahigh‐molecular‐weight polyethylene (UHMWPE) causes subsurface oxidation, which leads to failure in UHMWPE orthopedic components, yet the mechanisms causing subsurface oxidation remain unclear. The shelf aging of γ‐irradiated UHMWPE bars has been studied with electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) imaging and with microtoming and Fourier transform infrared microscopy. The bars initially contained only allyl radicals, and upon air exposure, a surface layer of peroxyl radicals formed through the reaction of allyl radicals with oxygen. Importantly, a band of low radical intensity just beneath the peroxyl layer became apparent. NMR imaging showed a zone of altered proton relaxation in this zone. With increasing time, surface peroxyl radicals persisted in comparison with the interior allyl radicals, although oxygen did not appear to penetrate any more deeply into the bar. The area of maximal oxidation and mechanical disruption, measured after 3 years, was at the interface between the zone of exterior peroxyl radicals and the zone of low radical intensity. We present a mechanism involving the intermediacy of sterically strained reactive dialkyl peroxides at this interface to explain subsurface oxidation. We also demonstrate that EPR and NMR imaging provides information that could potentially be used to identify subsurface oxidized UHMWPE components before failure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5929–5941, 2004     

Performance bounds for passive sensor arrays operating in a turbulent medium: plane-wave analysis

The performance bounds of a passive acoustic array operating in a turbulent medium with fluctuations described by a von Kármán spectrum are investigated. This treatment considers a single, monochromatic, plane-wave source at near-normal incidence. A line-of-sight propagation path is assumed. The primary interests are in calculating the Cramer-Rao lower bounds of the azimuthal and elevational angles of arrival and in observing how these bounds change with the introduction of additional unknowns, such as the propagation distance, turbulence parameters, and signal-to-noise ratio. In both two and three dimensions, it is found that for large values of the index-of-refraction variance, the Cramer-Rao lower bounds of the angles of arrival increase significantly at large values of the normalized propagation distance. For small values of the index-of-refraction variance and normalized propagation distance, the signal-to-noise ratio is found to be the limiting factor. In the two-dimensional treatment, it is found that the estimate of the angle of arrival will decouple from the estimates of the other parameters with the appropriate choice of array geometry. In three dimensions, again with an appropriate choice of array geometry, the estimates of the azimuth and elevation will decouple from the estimates of the other parameters, but due to the constraints of the model, will remain coupled to one another.