Dilute solution studies of nitrogen-substituted polyurethanes

A high molecular weight linear polyurethane was prepared by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). Varying amounts of the labile carbamate protons of the polyurethane backbone were substituted by a number of groups of varying length and composition. The resultant grafted or nitrogen-substituted polyurethanes were then studied viscometrically in both polymer solvent and in a polymer solvent—nonsolvent mixture. The configuration of the nitrogen-substituted polyurethane was found to be dependent upon the number and length of pendent branches.     

Speech intelligibility of normal listeners and persons with impaired hearing in traffic noise

Speech intelligibility (PB words) in traffic-like noise was investigated in a laboratory situation simulating three common listening situations, indoors at 1 and 4 m and outdoors at 1 m. The maximum noise levels still permitting 75% intelligibility of PB words in these three listening situations were also defined. A total of 269 persons were examined. Forty-six had normal hearing, 90 a presbycusis-type hearing loss, 95 a noise-induced hearing loss and 38 a conductive hearing loss. In the indoor situation the majority of the groups with impaired hearing retained good speech intelligibility in 40 dB(A) masking noise. Lowering the noise level to less than 40 dB(A) resulted in a minor, usually insignificant, improvement in speech intelligibility. Listeners with normal hearing maintained good speech intelligibility in the outdoor listening situation at noise levels up to 60 dB(A), without lip-reading (i.e., using non-auditory information). For groups with impaired hearing due to age and/or noise, representing 8% of the population in Sweden, the noise level outdoors had to be lowered to less than 50 dB(A), in order to achieve good speech intelligibility at 1 m without lip-reading.     

Dielectron widths of the Gamma(1S,2S,3S) resonances

We determine the dielectron widths of the Gamma(1S), Gamma(2S), and Gamma(3S) resonances with better than 2% precision by integrating the cross section of e+e- -->Gamma over the e+e- center-of-mass energy. Using e+e- energy scans of the Gamma resonances at the Cornell Electron Storage Ring and measuring Gamma production with the CLEO detector, we find dielectron widths of 1.252+/-0.004(sigma(stat))+/-0.019(sigma(syst)) keV, 0.581+/-0.004+/-0.009 keV, and 0.413+/-0.004+/-0.006 keV for the Gamma(1S), Gamma(2S), and Gamma(3S), respectively.     

Observation of psi(3770) --> pi pi J/psi and measurement of Gamma ee[psi(2S)

We observe signals for the decays psi(3770) --> XJ/psi from data acquired with the CLEO detector operating at the CESR e+ e- collider with square root of s = 3773 MeV. We measure the following branching fractions Beta(psi(3770) --> XJ/psi and significances: (189 +/- 20 +/- 20) x 10(-5) (11.6sigma) for X = pi+ pi-, (80 +/- 25 +/- 16) x 10(-5) (3.4sigma) for X = pi0 pi0, and (87 +/- 33 +/- 22) x 10(-5) (3.5sigma) for X = eta, where the errors are statistical and systematic, respectively. The radiative return process e+ e- --> gamma psi(2S) populates the same event sample and is used to measure Gamma ee[psi(2S)] = (2.54 +/- 0.03 +/- 0.11) keV.     

Experimental limits on weak annihilation contributions to decays

We present the first experimental limits on high-q2 contributions to charmless semileptonic decays of the form expected from the weak annihilation (WA) decay mechanism. Such contributions could bias determinations of /Vub/ from inclusive measurements of B-->Xulupsilon. Using a wide range of models based on available theoretical input we set a limit of GammaWA/Gammab-->u<7.4% (90% confidence level) on the WA fraction, and assess the impact on previous inclusive determinations of /Vub/.     

Hydration and interfacial water in Nafion membrane probed by transmission infrared spectroscopy

Infrared spectroscopy was applied to probe water inside pores and channels of Nafion membrane exchanged with either proton (H+) or sodium ions (Na+). Transmission measurements were performed on freestanding Nafion 112 (approximately 50 microm thickness) in a cell that enabled adjustment of the relative humidity. Experiments that employed Na+-exchanged Nafion focused on relative humidity environments at or below about 32% generated through the use of humectants. Under these conditions, narrow features in the O-H stretching spectral region near 3650-3720 cm(-1), previously attributed to interfacial water, were detected and matched to bands in vibrational sum frequency (VSF) spectra of water/air, water/organic, and salt-solution/air interfaces. The features correspond to the stretching mode of the "free" OH group of water oriented with one hydrogen atom toward other water molecules and interacting through hydrogen bonding and the other straddling the interface extending into fluorocarbon-rich regions (approximately 3668 cm(-1)) or air-filled segments (approximately 3700 cm(-1)) in the membrane. For membrane exchanged with H+, -SO3- groups were easily shifted to -SO3H as water was removed upon exposure to a few Torr of vacuum at 95 degrees C. In contrast, residual water was retained by membrane exchanged with Na+ after exposure to these conditions for up to 72 h. The permeation of methanol and acetone into Na+-exchanged Nafion 112 was also examined. The C-H and O-H stretching modes of methanol were perturbed in a manner that suggests the polymer disrupts hydrogen bonding interactions within the solvent, similar to the effect it exerts on pure water. For acetone, the C-H stretching modes were not shifted appreciably compared to those of the bulk liquid. However, the carbonyl band was affected, indicating the likely importance of dipolar interactions between solvent molecules and polar groups on the polymer. Control experiments performed with poly(hexafluoropropylene-co-tetrafluoroethylene) (FEP) membrane did not show evidence for water or methanol permeation, which demonstrates the critical role played by the ion-filled channels and pores in facilitating solvent transport within Nafion membrane.     

X-ray microprobe of orbital alignment in strong-field ionized atoms

We have developed a synchrotron-based, time-resolved x-ray microprobe to investigate optical strong-field processes at intermediate intensities (10(14) - 10(15) W/cm2). This quantum-state specific probe has enabled the direct observation of orbital alignment in the residual ion produced by strong-field ionization of krypton atoms via resonant, polarized x-ray absorption. We found strong alignment to persist for a period long compared to the spin-orbit coupling time scale (6.2 fs). The observed degree of alignment can be explained by models that incorporate spin-orbit coupling. The methodology is applicable to a wide range of problems.     

Three Point Boundary Value Problems on Time Scales

This work formulates existence theorems for solutions to three-point boundary value problems on time scales. The ideas are based on a relationship between the three point boundary conditions, lower and upper solutions and topological degree theory.     

Europium Oxychloride Absorption Spectroscopy as an Optical Probe of Temperature

The temperature dependence of the features which arise from the ⁷F_0,1 → ⁵D₃ absorption transitions in EuOCl as seen by diffuse-reflectance spectroscopy has been investigated. The transitions shift linearly to higher energy with increasing temperature. The ratio of the intensities of the transitions arising from the ⁷F₀ state to those arising from the ⁷F₁ state also appears to be a linear function of temperature.     

Stable,Reactive, and Orthogonal Tetrazines: Dispersion Forces Promote the Cycloaddition with Isonitriles

The isocyano group is a structurally compact bioorthogonal functional group that reacts with tetrazines under physiological conditions. Now it is shown that bulky tetrazine substituents accelerate this cycloaddition. Computational studies suggest that dispersion forces between the isocyano group and the tetrazine substituents in the transition state contribute to the atypical structure–activity relationship. Stable asymmetric tetrazines that react with isonitriles at rate constants as high as 57 L mol^?1 s^?1 were accessible by combining bulky and electron‐withdrawing substituents. Sterically encumbered tetrazines react selectively with isonitriles in the presence of strained alkenes/alkynes, which allows for the orthogonal labeling of three proteins. The established principles will open new opportunities for developing tetrazine reactants with improved characteristics for diverse labeling and release applications with isonitriles.