New Coumarin and Bioactive Constituents of Chionanthus retusus

Chemistry of Natural Compounds - A new coumarin derivative, 7-O-methylparamicoumarin A (1), has been isolated from the roots of Chionanthus retusus, together with seven known compounds. The...     

Photoviscoelastic behavior of amorphous polymers during transition from the glassy to rubbery state

Tensile stress‐relaxation experiments with simultaneous measurements of Young's relaxation modulus, E, and the strain‐optical coefficient, C_?, were performed on two amorphous polymers—polystyrene (PS) and polycarbonate (PC)—over a wide range of temperatures and times. Master curves of these material functions were obtained via the time‐temperature superposition principle. The value of C_? of PS is positive in the glassy state at low temperature and time; then it relaxes and becomes negative and passes through a minimum in the transition zone from the glassy to rubbery state at an intermediate temperature and time and then monotonically increases with time, approaching zero at a large time. The stress‐optical coefficient of PS is calculated from the value of C_?. It is positive at low temperature and time, decreases, passes through zero, becomes negative with increasing temperature and time in the transition zone from the glassy to rubbery state, and finally reaches a constant large negative value in the rubbery state. In contrast, the value of C_? of PC is always positive being a constant in the glassy state and continuously relaxes to zero at high temperature and time. The value of C_σ of PC is also positive being a constant in the glassy state and increases to a constant value in the rubbery state. The obtained information on the photoelastic behavior of PS and PC is useful for calculating the residual birefringence and stresses in plastic products. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2252–2262, 2001     

Electronic specific heat of nanographite ribbons

The electronic specific heat of nanographite ribbons exhibits rich temperature dependence, mainly owing to the special band structures. The thermal property strongly depends on the geometric structures, the edge structure and the width. There is a simple relation between the ribbon width and the electronic specific heat for the metallic or semiconducting armchair ribbons. However, it is absent for the zigzag ribbons. The metallic armchair ribbons exhibit linear temperature dependence. The semiconducting armchair ribbons exhibit composite behavior of power and exponential functions. As for the zigzag ribbons, the temperature dependence of the specific heat is proportional to T^1−p. The value of p quickly increases from to 1 as the ribbon width gradually grows. The zigzag ribbons might be the first system which exhibits the novel temperature dependence. The nanographite ribbons differ from an infinite graphite sheet, which illustrates that the finite-size effects are significant.     

Reducing the bias and uncertainty of free energy estimates by using regression to fit thermodynamic integration data

This report presents the application of polynomial regression for estimating free energy differences using thermodynamic integration data, i.e., slope of free energy with respect to the switching variable λ. We employ linear regression to construct a polynomial that optimally fits the thermodynamic integration data, and thus reduces the bias and uncertainty of the resulting free energy estimate. Two test systems with analytical solutions were used to verify the accuracy and precision of the approach. Our results suggest that use of regression with high degree of polynomials provides the most accurate free energy difference estimates, but often with slightly larger uncertainty, compared to commonly used quadrature techniques. High degree polynomials possess the flexibility to closely fit the thermodynamic integration data but are often sensitive to small changes in the data points. Thus, we also used Chebyshev nodes to guide in the selection of nonequidistant λ values for use in thermodynamic integration. We conclude that polynomial regression with nonequidistant λ values delivers the most accurate and precise free energy estimates for thermodynamic integration data for the systems considered here. Software and documentation is available at http://www.phys.uidaho.edu/ytreberg/software . © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

The scope and limitations of 1,3-stannyl shift-promoted intramolecular cyclizations of alpha-stannyl radicals with a formyl group

Alpha-tributylstannyl radicals can be generated from the corresponding bromides or xanthates. These radicals undergo efficient intramolecular 1,5-cyclizations with a formyl group. The resulting beta-stannyl alkoxy radicals proceed through a 1,3-stannyl shift from carbon to oxygen to afford beta-stannyloxy radicals. This novel rearrangement is most likely irreversible and serves as a driving force to promote the cyclizations. Although the cyclization rates can be accelerated when the formyl group carries alpha-dimethyl substituents, unfortunately beta-scission of the alkoxy radicals becomes competitive with the 1,3-stannyl shift. The beta-stannyloxy radicals can be employed in further cyclizations to obtain tandem cyclization products.     

Star number and star arboricity of a complete multigraph

Let G be a multigraph. The star number s(G) of G is the minimum number of stars needed to decompose the edges of G. The star arboricity sa(G) of G is the minimum number of star forests needed to decompose the edges of G. As usual λK _n denote the λ-fold complete graph on n vertices (i.e., the multigraph on n vertices such that there are λ edges between every pair of vertices). In this paper, we prove that for n ⩾ 2

Characterization of ring‐opening polymerization of genipin and pH‐dependent cross‐linking reactions between chitosan and genipin

In this study, a novel chitosan‐based polymeric network was synthesized by crosslinking with a naturally occurring crosslinking agent—genipin. The results showed that the crosslinking reactions were pH‐dependent. Under basic conditions, genipin underwent a ring‐opening polymerization prior to crosslinking with chitosan. The crosslink bridges consisted of polymerized genipin macromers or oligomers (7 ～ 88 monomer units). This ring‐opening polymerization of genipin was initiated by extracting proton from the hydroxyl groups at C‐1 of deoxyloganin aglycone, followed by opening the dihydropyran ring to conduct an aldol condensation. At neutral and acidic conditions, genipin reacted with primary amino groups on chitosan to form heterocyclic amines. The heterocyclic amines were further associated to form crosslinked networks with short chains of dimmer, trimer, and tetramer bridges. An accompanied reaction of nucleophilic substitution of the ester group on genipin by the primary amine group on chitosan would occur in the presence of an acid catalysis. The extent in which chitosan gels crosslinked with genipin was significantly dependent on the crosslinking pH values: 39.9 ± 3.8% at pH 5.0, 96.0 ± 1.9% at pH 7.4, 45.4 ± 1.8% at pH 9.0, and 1.4 ± 1.0% at pH 13.6 (n = 5, p < 0.05). Owing to the different crosslinking extents and different chain lengths of crosslink bridges, the genipin‐crosslinked chitosan gels showed significant difference in their swelling capability and their resistance against enzymatic hydrolysis, depending on the pH conditions for crosslinking. These results indicated a direct relationship between the mode of crosslinking reaction, and the swelling and enzymatic hydrolysis properties of the genipin‐crosslinked chitosan gels. The ring‐opening polymerization of genipin and the pH‐dependent crosslinking reactions may provide a novel way for the preparation and exploitation of chitosan‐based gels for biomedical applications. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1985–2000, 2005     

A new component mode synthesis method: Quasi-static mode compensation

A new component mode synthesis method is presented in this paper that combines the computational efficiency of the well-known constraint mode approach with the dynamic compensation accuracy obtained by higher-order expansion methods. Instead of employing static constraint modes, quasi-static modes are used to capture inertial effects of the truncated modes. The method is ideally suited for mid-band frequency analysis in which both high-frequency and low-frequency modes may be omitted. A tuning parameter, designated as the centering frequency, controls the dynamic range of the quasi-static modes. Numerical examples are provided which demonstrate the improved accuracy of the proposed method.