Deprotection of heteroaromatic carbamates via a base-catalyzed methanolysis

A simple and mild method for the deprotection of heteroaromatic carbamates via methanolysis using a catalytic amount of base such as sodium methoxide, DBU, or Verkade’s base (proazaphosphatranes) is presented. Carbamate protecting group of an aliphatic amine is not affected under these conditions.     

Local order in polycarbonate glasses by 13C{19F} rotational‐echo double‐resonance NMR

Nearest‐neighbor chain packing in a homogeneous blend of carbonate ¹³C‐labeled bisphenol A polycarbonate and CF₃‐labeled bisphenol A polycarbonate has been characterized using a shifted‐pulse version of magic‐angle spinning ¹³C{¹⁹F} rotational‐echo double‐resonance (REDOR) NMR. Complementary NMR experiments have also been performed on a polycarbonate homopolymer containing the same ¹³C and ¹⁹F labels. In the blend, the ¹³C observed spin was at high concentration, and the ¹⁹F dephasing or probe spin was at low concentration. In this situation, an analysis in terms of a distribution of isolated heteronuclear pairs of spins is valid. A comparison of the results for the blend and homopolymer defines the NMR conditions under which higher concentrations of probe labels can be used and a simple analysis of the REDOR results is still valid. The nearest neighbors of a CF₃ on one chain generally include a carbonate group on an adjacent chain. A direct interpretation of the REDOR total dephasing for the polycarbonate blend indicates that at least 75% of carbonate‐carbon ¹³C ··· F₃ nearest neighbors are separated by a narrow distribution of distances 4.7 ± 0.3 Å. In addition, analysis of the variations in REDOR spinning‐sideband dephasing shows that most of the ¹³C ··· F₃ dipolar vectors have a preferred orientation relative to the polycarbonate mainchain axis. This combination of distance and orientational constraints is interpreted in terms of local order in the packing of the carbonate group of one polycarbonate chain relative to the isopropylidene moiety in a neighboring chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2760–2775, 2006     

Random optimizations for direct heteronuclear correlations

A novel optimization method is described for the acquisition of direct one‐bond heteronuclear correlations. The RDSQC (Randomly optimized Direct correlation Single Quantum Coherence) experiment utilizes an optimization based on the randomly ordered sampling of a range of couplings. The random order of the l/(2*(¹J_CHmin)) delays removes the signal dependency on a single type of apodization, thus eliminating a significant portion of the F₁ artifacts induced in the accordion‐optimized ADSQC experiment. Compared to the statically optimized GHSQC, the randomly optimized data maintains the desired signal intensity in most cases, with a small loss for the weakly coupled proton‐carbon pairs and significant gains for the more strongly coupled pairs. Compared to the accordion‐optimized ADSQC data, the randomly optimized data afforded similar signal‐to‐noise without the F₁ modulated artifacts simplifying spectral interpretation.     

Computations for the familial analysis of binary traits

For familial aggregation of a binary trait, one method that has been used is the GEE2 (generalized estimating equation) method corresponding to a multivariate logit model. We solve the complex estimating equations for the GEE2 method using an automatic differentiation software which computes the derivatives of a function numerically using the chain rule of the calculus repeatedly on the elementary operations of the function. Based on this, we are able to show in a simulation study that the GEE2 estimates are quite close to the maximum likelihood estimates assuming a multivariate logit model, and that the GEE2 method is computationally faster when the dimension or family size is larger than four.     

Correlation at Low Temperature: II. Asymptotics

The present paper is a continuation of ref. 4, where the truncated two-point correlation function for a class of lattice spin systems was proved to have exponential decay at low temperature, under a weak coupling assumption. In this paper we compute the asymptotics of the correlation function as the temperature goes to zero. This paper thus extends ref. 3 in two directions: The Hamiltonian function is allowed to have several local minima other than a unique global minimum, and we do not require translation invariance of the Hamiltonian function. We are in particular able to handle spin systems on a general lattice.     

Optimization of Enzymatic Clarification of Sapodilla Juice: A Statistical Perspective

Response surface methodology (RSM) was employed to establish optimum conditions for enzymatic clarification of sapodilla juice. Polygalacturonase obtained from Streptomyces lydicus had been purified to homogeneity and was used for the treatment. The independent variables were temperature (30–45 °C), enzyme concentration (0.5–1.5 U), and treatment time (30–90 min), whose effects on viscosity and clarity of the juice were evaluated using a Box–Behnken design. Significant regression models describing the changes of viscosity and clarity with respect to the independent variables were obtained, with the coefficient of determination, R ² , greater than 0.8. Based on response surfaces and contour plots, the optimum conditions for clarifying sapodilla juice were enzyme concentration 1.15 U, incubation temperature 34 °C, and incubation time 70 min.     

Increase and decrease of tunneling by variation of the barrier height

We show, based on some results from classical analysis, that time-dependent perturbations can either increase or decrease the tunneling probability. The results depend on the form of the function T(√V), where T is the transmission coefficient and V the potential. If T(√V) is convex, the perturbation will always result in a decrease of the tunneling; if T(√V) is concave, both increase as well as decrease occur.