Stable Pyrrole-Linked Bioconjugates through Tetrazine-Triggered Azanorbornadiene Fragmentation

An azanorbornadiene bromovinyl sulfone reagent for cysteine-selective bioconjugation has been developed. Subsequent reaction with dipyridyl tetrazine leads to bond cleavage and formation of a pyrrole-linked conjugate. The latter involves ligation of the tetrazine to the azanorbornadiene-tagged protein through inverse electron demand Diels–Alder cycloaddition with subsequent double retro-Diels–Alder reactions to form a stable pyrrole linkage. The sequence of site-selective bioconjugation followed by bioorthogonal bond cleavage was efficiently employed for the labelling of three different proteins. This method benefits from easy preparation of these reagents, selectivity for cysteine, and stability after reaction with a commercial tetrazine, which has potential for the routine preparation of protein conjugates for chemical biology studies.     

Simplicity of vacuum modules over affine Lie superalgebras

We prove an explicit condition on the level k for the irreducibility of a vacuum module $V^k$ over a (non-twisted) affine Lie superalgebra, which was conjectured by M. Gorelik and V.G. Kac. An immediate consequence of this work is the simplicity conditions for the corresponding minimal W-algebras obtained via quantum reduction, in all cases except when the level k is a non-negative integer.     

Direct excitation of the forbidden clock transition in neutral 174Yb atoms confined to an optical lattice

We report direct single-laser excitation of the strictly forbidden (6s2)1S0 <--> (6s6p)3P0 clock transition in 174Yb atoms confined to a 1D optical lattice. A small (approximately 1.2 mT) static magnetic field was used to induce a nonzero electric dipole transition probability between the clock states at 578.42 nm. Narrow resonance linewidths of 20 Hz (FWHM) with high contrast were observed, demonstrating a resonance quality factor of 2.6 x 10(13). The previously unknown ac Stark shift-canceling (magic) wavelength was determined to be 759.35 +/- 0.02 nm. This method for using the metrologically superior even isotope can be easily implemented in current Yb and Sr lattice clocks and can create new clock possibilities in other alkaline-earth-like atoms such as Mg and Ca.     

Quantitative parameter-free prediction of simulated crystal-nucleation times

We present direct comparisons between simulated crystal-nucleation times and theoretical predictions using a model of aluminum, and demonstrate that a quantitative prediction can be made. All relevant thermodynamic properties of the system are known, making the agreement of our simulation data with nucleation theories free of any adjustable parameters. The role of transient nucleation is included in the classical nucleation theory approach, and shown to be necessary to understand the observed nucleation times. The calculations provide an explanation on why nucleation is difficult to observe in simulations at moderate undercoolings. Even when the simulations are significantly larger than the critical nucleus, and when simulation times are sufficiently long, at moderate undercoolings the small concentration of critical nuclei makes the probability of the nucleation low in molecular dynamics simulations.     

Reactive lyotropic polyimide oligomers

Amine-terminated and maleimide-terminated oligomers of molecular weight 1200–1800 based on 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl and 3,3′,4,4′-biphenylenetetracarboxylic dianhydride were synthesized and characterized for lyotropic liquid crystalline behavior. Several different synthetic procedures were evaluated and a one-step procedure in m-cresol was found to be the most effective for producing fully imidized materials. Lyotropic behavior was observed only for the as-prepared solutions in m-cresol and in dilutions of this solution. Oligomer thermal stability was excellent, onsets of decomposition were in excess of 550°C. © 1996 John Wiley & Sons, Inc.     

RANDOM RESPONSE OF PREISACH HYSTERETIC SYSTEMS

An approximate method for analyzing the response of Preisach hysteretic systems with non-local memory under stationary Gaussian excitation is proposed. The covariance matrix equation of system response is derived. The cross correlation function of Preisach hysteretic force and response in the covariance equation is evaluated based on the switching probability analysis and the Gaussian approximation of response process and an explicit expression for the cross correlation function is given for the case of symmetric Preisach weighting function. It is shown that the numerical result obtained by using the proposed method is in good agreement with that from digital simulation.     

STOCHASTIC AVERAGING OF STRONGLY NON-LINEAR OSCILLATORS UNDER BOUNDED NOISE EXCITATION

A stochastic averaging method for strongly non-linear oscillators under external and/or parametric excitation of bounded noise is proposed by using the so-called generalized harmonics functions. The method is then applied to study the primary resonance of Duffing oscillator with hardening spring under external excitation of bounded noise. The stochastic jump and its bifurcation of the system are observed and explained by using the stationary probability density of amplitude and phase. Subsequently, the method is applied to study the dynamical instability and parametric resonance of Duffing oscillator with hardening spring under parametric excitation of bounded noise. The primary unstable region is delineated by evaluating the Lyapunov exponent of linearized system, and the response and jump of non-linear system around the unstable region are examined by using the sample functions and stationary probability density of amplitude and phase.     

Synthetic studies on the ingenane diterpenes. An improved entry into a trans-intrabridgehead system

[reaction: see text] The efficient construction of an ingenol intermediate exhibiting "insideminus signoutside" intrabridgehead stereochemistry is reported. The sequence features the net conversion of a cis-intrabridgehead compound into a highly strained trans-species via palladium-mediated isomerization of an allylic epoxide followed by a low-temperature alkoxide-accelerated 1,5-hydrogen migration.     

Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors

This contribution reports light responsive catalytic nanoreactors based on poly(2-oxazoline) diblock copolymers. The hydrophobic block of the copolymer is a random copolymer consisting of a spiropyran functionalized 2-oxazoline (SPOx) and 2-(but-3-yn-1-yl)-4,5-dihydrooxazole (ButynOx), while the hydrophilic block is based on 2-methyl-2-oxazoline (MeOx). The block copolymer is terminated with tris(2-aminoethyl) amine (TREN) that serves as catalyst in a Knoevenagel condensation. Four block copolymers with different ButynOx/SPOx and hydrophilic/hydrophobic ratios are synthesized and self-assembled through solvent exchange. Micelles and vesicles of various sizes are observed by TEM, which undergo morphological and size changes in response to irradiation with UV light. We hypothesize that these transformations in the nanostructures are caused by increases in the hydrophilicity of the hydrophobic block when spiropyran (SP) isomerizes to merocyanine (MC) in the presence of UV light. The reversible transition from micellar to vesicular nanoreactors resulted in increased reaction kinetics through improved substrate accessibility to the catalytic site, or termination of the catalytic reaction due to polymer precipitation. These nanoreactors present a promising platform towards photoregulating reaction outcomes based on changes in nanostructure morphology.