Dynamic Ion Speciation during the Hydrolysis of Aryltrifluoroborates**

Organotrifluoroborates serve as coupling partners during transmetalation in the Suzuki–Miyaura reaction but require hydrolysis prior to the coupling reaction. Their anionic nature allows study of their hydrolysis by electrospray ionization mass spectrometry (ESI-MS) through real-time monitoring, complemented by pH analysis. The induction period varied according to the borates employed, and a dynamic series of equilibria for numerous ions was observed during hydrolysis. We found that the induction periods and reaction rates were sensitive to the R group of the borates, the shape of the reaction vessel, and stir rate.     

Photoprotection of Mammalian Acid-Soluble Collagen by Cuttlefish Sepia Melanin In Vitro

Several important clinical conditions can result in close association between the pigment melanin and dermal collagen. Because melanin and its precursors can be chemically reactive in ground and excited states, it is important to know whether the resulting melanin-collagen interaction results in photoprotection or photoaggression. Acidic and neutral air-saturated collagen suspensions (0.033%) were irradiated with0–2.6 times 104 J/m2 UVC or with0–83 times 104 J/m2 solar-simulating UV radiation (SSR). Photochemical destruction of a photolabile collagen fluorophore (δ_em 360 nm) and collagen chain degradation were monitored as functions of irradiation time in the presence and absence of added (0–100μg) sepia eumelanin. Melanin retarded collagen photodamage but did not qualitatively alter the fluorescence fading kinetics. Both H202 and 02 can be produced by UV irradiation of eumelanin. Added H202 and K02 destroyed collagen fluorescence and caused 50% chain degradation at ca10–20-fold molar excess. Previous studies have demonstrated that eumelanins efficiently scavenge 02 . We demonstrated that eumelanin also efficiently scavenges H202 as evidenced by its ability to (a) compete with scopoletin for peroxide uptake and (b) directly take up H202 through a dialysis bag. The latter observation suggests that peroxide scavenging could occur in vivo by melanin sequestered in melanophages. Thus, neither UV-generated 02 nor H202 are likely to be present in concentrations high enough to cause measurable collagen damage. Absorption and/or scattering of excitation radiation away from the target chromophore appears to be the primary photoprotection mechanism, although scavenging of active 02 intermediates may play an important, if subtle role.     

Isoperimetric constants of manifolds with small handles

Mathematische Zeitschrift -     

The equation of state of solid molecular hydrogen and deuterium

Isochores of solid H₂ and D₂ have been measured to 2 kbar. Our results lead to reevaluation of the 4.2 K isotherm of Anderson and Swenson to 25 kbar. The equation of state has been determined, including ortho-para dependence. The pre-melting phase transition cited in recent russian literature has not been detected.     

Mixed-mode failure of composite laminates with cracks

The behavior of quasi-isotropic graphite/epoxy laminates with cracks subjected to various biaxial-stress fields was studied experimentally. This was accomplished by uniaxial tensile loading of specimens with cracks of various orientations with the loading axis. It was found that the critical stress-intensity factor, based on a projected crack length increased by a characteristic damage dimension, is nearly constant with stress biaxiality and initial crack length. Paper was presented at V International Congress on Experimental Mechanics held in Montreal, Quebec, Canada on June 10–15, 1984.     

O,N,N'-trialkylisoureas as mild activating reagents for N-acylsulfonamide anchors

[chemical reaction: see text]. Prior to detachment of compounds synthesized on sulfonamide based safety-catch linkers, the molecular anchor has to be activated. This is achieved by alkylation of the nitrogen atom of the N-acylsulfonamide using different established protocols. As an addition to the existing repertoire of activating reagents, we suggest the use of O,N,N'-trialkylisoureas. Besides the demonstration of the feasibility of these mild alkylating agents for this purpose, custom-tailored novel O,N,N'-trialkylisoureas prepared from electron-deficient alcohols are reported.     

Test by NMR of the phase coherence of electromagnetically induced transparency

Electromagnetically induced transparency is an effect observed in atomic systems, originating from quantum interference, in which electromagnetic transitions to and from a certain quantum state become suppressed. This dark state is also characterized by a quantum phase, relative to other states, which theoretically should stop evolving, but remain phase coherent, during transparency. We test this theoretical prediction using techniques developed for liquid-state nuclear magnetic resonance quantum computation, applied to a spin-7/2 nuclear spin system. A sequence of quantum operations is applied to create the dark state, and during transparency its phase evolution is measured relative to a reference state using Ramsey interferometry. Experimental measurements of the fringe visibility are in excellent agreement with theoretical expectations, taking into account measured decoherence rates.