An information-theoretic characterization of partitioned property spaces

A methodology, derived by analogy to Shannon’s information-theoretic theory of communication and utilizing the concept of mutual information, has been developed to characterize partitioned property spaces. A family of non-intersecting subsets that cover the “universe” of objects represents a partitioned property space. Each subset is thus an equivalence class. A partition and it’s associated equivalence classes can be generated using any one of a number of procedures including hierarchical and non-hierarchical clustering, direct approaches using rough set methods, and cell-based partitioning, to name a few. Thus, partitioned property spaces arise in many instances and represent a very large class of problems. The approach is based on set-valued mappings from equivalence classes in one partition to those in another and provides a coarse-grained means for comparing property spaces. From these mappings it is possible to compute a number of Shannon entropies that afford calculation of mutual information, which represents that amount of information shared by two partitions of a set of objects. Taking the ratio of the mutual information with the maximum possible mutual information yields a quantity that measures the similarity of the two partitions. While the focus in this work is directed towards small sets of objects the approach can be extended to many more classes of problems that can be put into a similar form, which includes many types of cheminformatic and biological problems. A number of scenarios are presented that illustrate the concept and indicate the broader class of problems that can be handled by this method.     

Photoisomerization dynamics of azobenzene in solution with S1 excitation: a femtosecond fluorescence anisotropy study

Measurements of anisotropy of femtosecond fluorescence after direct excitation of the S1(n,pi*) state of azobenzene in hexane and ethylene glycol solutions have been carried out to address the controversy about inversion and rotation in the mechanism of photoisomerization. The observed anisotropies in hexane decay to a nonzero asymptotic level with a relaxation period the same as that for slow decay of the corresponding biexponential transient; this effect is attributed to involvement of the out-of-plane CNNC-torsional motion on approach to a twisted conical intersection along the "rotation channel" that depolarizes the original in-plane transition moment. In contrast, when the rotational channel becomes substantially hindered in ethylene glycol, the anisotropies show no discernible decay feature, but the corresponding transients show prominent decays attributed to involvement of in-plane symmetric motions; the latter approach a planar-sloped conical intersection along a "concerted inversion channel" for efficient internal conversion through vibronic coupling. The proposed mechanism is consistent with theoretical calculations and rationalizes both results on quantum yields and ultrafast observations.     

Proline-mediated dimerization of cinnamaldehydes via 1,3-dipolar cycloaddition reaction with azomethine ylides. A rapid access to highly functionalized hexahydro-1H-pyrrolizine

1,3-Dipolar cycloaddition reaction of cinnamaldehyde with azomethine ylides generated through decarboxylation of iminium or oxazolidinone intermediate formed by the reaction of l-proline with cinnamaldehydes is reported. The stereoselective reaction provides an efficient access to the highly functionalized hexahydro-1H-pyrrolizine.     

Coma compensation of o-ring driven liquid-filled lenses

The purpose of this study was to analyze the coma compensation of bi-convex o-ring driven liquid-filled lenses. In a previous study, the o-ring driven liquid-filled lens was composed of a base plate, a glass covered liquid container, an elastic membrane, an o-ring, a spring, and three hand-driven screws. The movement of the ring is used to control the focal length or the focus position. However, the o-ring driven liquid lens exhibited a coma effect when trying to use it to tilt the direction of light. To resolve this problem, in this study the bi-convex o-ring driven liquid-filled lens was constructed of two single o-ring driven liquid-filled lenses, and a coma compensation analysis of this new design is carried out. zemax software was used to construct the model, and the Zernike polynomials were used to estimate the compensation result. According to the simulation results, the following two actions could compensate for the initial coma aberration: (1) the same tilt direction of the front and back lenses; (2) increased the curvature of the back lens.     

Preparation of electroactive silica mesopores by encapsulating polyaniline chains into silica framework via nonsurfactant templating sol-gel route

Electroactive silica mesopores have been synthesized by encapsulating different loadings of polyaniline chains into a silica network through sol-gel reactions of TEOS in the presence of polyaniline latex with D-glucose. It should be noted that the electroactive silica mesopores at higher polyaniline loading was found to reveal higher surface areas, larger pore volume, and slightly larger pore diameters as compared to that of neat non-electroactive silica mesopores.     

Mercuric acetate-mediated annulation of homopropargylic alcohols having thioether substituent. A general route for the synthesis of tetrasubstituted furans from propargylic dithioacetals

Treatment of an alkyl-substituted propargylic dithioacetal with ⁿBuLi followed by an aldehyde furnishes thio-substituted homopropargylic alcohol 7 which undergoes annulation in the presence of two equivalents of mercury acetate to give the corresponding mercurio-substituted furan 12. Reaction of 12 with iodine gives iodofuran in moderate to good yield.     

Fluorescent organic nanoparticles of benzofuran-naphthyridine linked molecules: formation and fluorescence enhancement in aqueous media

[structure: see text] Ethynyl-linked benzofuran-naphthyridine compounds show high-yield fluorescence with solvatochromic properties. One of the compounds, ABAN, has successfully formed fluorescent organic nanoparticles (FONs), for which the photophysical properties such as the spectral features and intensity are remarkably different from those at the molecular level (solution) and in bulk material. The results are tentatively rationalized by the FONs inducing coplanarization of the benzofuran-naphthyridine molecule to extend its effective conjugation length and hence increase the oscillator strength.