LIFETIME AND ACTIVATION ENERGY OF THE PHOTOINDUCED QUINOID INTERMEDIATE IN PYRIDOXAL CATALYSIS

Abstract— The lifetime of the p -quinoid intermediate of transamination was determined through photoinduction in the metal-ion model system. From the dependence of the lifetime on temperature, the Arrhenius activation energy for proton transfer was 4.2–8.4 kJ/mol (1-2 kcal/mol). The activation energy correlated well with the R group of the amino acid and demonstrated that native substrates have a very labile proton.     

Structure and properties of poly(ethylene terephthalate) crystallized by converging flow and high pressure

The structure and properties of a poly(ethylene terephthalate) extrudate, prepared by converging flow and high pressure, were examined. Relatively high levels of crystallinity and orientation were produced by the combination of an orienting flow and high-pressure quench. The fine structure was examined in detail by x-ray diffraction, negative staining–transmission electron microscopy, and amine etching–gel permeation chromatography. The morphology was directly relatable to this unique preparative technique. Modulus was determined by a compressive Rheovibron technique. Low shrinkage and the compressive modulus were related to the structure in the development of a structural model.     

Multicomponent Organic Metal Halide Hybrid with White Emissions

Zero‐dimensional (0D) organic metal halide hybrids, in which organic and metal halide ions cocrystallize to form neutral species, are a promising platform for the development of multifunctional crystalline materials. Herein we report the design, synthesis, and characterization of a ternary 0D organic metal halide hybrid, (HMTA)₄PbMn_0.69Sn_0.31Br₈, in which the organic cation N‐benzylhexamethylenetetrammonium (HMTA⁺, C₁₃H₁₉N₄⁺) cocrystallizes with PbBr₄^2?, MnBr₄^2?, and SnBr₄^2?. The wide band gap of the organic cation and distinct optical characteristics of the three metal bromide anions enabled the single‐crystalline “host–guest” system to exhibit emissions from multiple “guest” metal halide species simultaneously. The combination of these emissions led to near‐perfect white emission with a photoluminescence quantum efficiency of around 73 %. Owing to distinct excitations of the three metal halide species, warm‐ to cool‐white emissions could be generated by controlling the excitation wavelength.     

Sound velocity anomalies near the spin glass transition in an austenitic stainless steel alloy

A cusp in the magnetic susceptibility temperature dependence of a commercial manganese austenitic stainless steel alloy, attributable to spin-glass condensation, is accompanied by anomalies in the temperature dependences of both longitudinal and transverse ultrasonic wave velocities.     

Nonlinear amplification of small spin precession using long-range dipolar interactions

In measurements of small signals using spin precession the precession angle usually grows linearly in time. We show that a dynamic instability caused by spin interactions can lead to an exponentially growing spin-precession angle, amplifying small signals and raising them above the noise level of a detection system. We demonstrate amplification by a factor of greater than 8 of a spin-precession signal due to a small magnetic field gradient in a spherical cell filled with hyperpolarized liquid 129Xe. This technique can improve the sensitivity in many measurements that are limited by the noise of the detection system, rather than the fundamental spin-projection noise.     

Elastic constants of natural quartz

The elastic constants of a natural-quartz sphere using resonance-ultrasound spectroscopy (RUS) are measured. The measurements of the near-traction-free vibrational frequencies of the sphere are matched with the predicted frequencies from the dynamic theory of elasticity, with optimized estimates for the elastic constants driving the differences between these sets of frequencies to a minimal value. The present computational model, although based on earlier approaches, is the first application of RUS to trigonal-symmetry spheres. Quartz shows six independent elastic constants, and our estimates of these constants are close to those computed by other means. Except for C14, after a 1% mass-density correction, natural quartz and cultured quartz show the same elastic constants. Natural quartz shows higher internal frictions.     

Enhancement of SQUID-detected NMR signals with hyperpolarized liquid 129Xe in a 1 microT magnetic field

We report an enhancement of proton NMR signals by a factor of 10(6) by cross polarization with hyperpolarized liquid 129Xe in an ultralow magnetic field of 1 microT. The NMR signals from cyclopentane, acetone, and methanol are detected using a commercial high-T(c) SQUID magnetometer with a signal-to-noise ratio of up to 1000 from a single 90 degrees tipping pulse. This technique allows a wide range of low-field NMR measurements and is promising for the detection of intermolecular scalar spin-spin couplings. Scalar intermolecular couplings can produce a shift of the average NMR frequency in a hyperpolarized sample even in the presence of rapid chemical exchange.     

Transverse spin relaxation in liquid 129Xe in the presence of large dipolar fields

Using spin-echo NMR techniques we study the transverse spin relaxation of hyperpolarized liquid 129Xe in a spherical cell. We observe an instability of the transverse magnetization due to dipolar fields produced by liquid 129Xe, and find that imperfections in the pi pulses of the spin-echo sequence suppress this instability. A simple perturbative model of this effect is in good agreement with the data. We obtain a transverse spin relaxation time of 1300 sec in liquid 129Xe, and discuss applications of hyperpolarized liquid 129Xe as a sensitive magnetic gradiometer and for a permanent electric dipole moment search.