Studies in the Sandalwood Oil Series. III. Chain Effect on Terpene Transformations

The carboxyl chain of some molecules has been found to be responsible for causing rearrangements and controlling their course. This chain effect, which operates during reactions involving carbonium ions, is illustrated with examples from Sandalwood oil chemistry.

Studies in the sandalwood-oil series. I. The structure, synthesis, and configuration of the lactone of tricycloekasantalic acid

The structure, synthesis, and configuration of the lactone of tricycloekasantalic acid have been described. It has been shown that in the formation of this lactone (XII) from the acids (I) or (II) a rearrangement is involved.

A Series of Cu-II-Azide Polymers of Cu-6 Building Units and the Role of Chelating Diamine in Controlling their Dimensionality: Synthesis, Structures, and Magnetic Behavior

Four new neutral copper-azido polymers Cu-6(N-3)(12)(aem)(2)](n)(1), Cu-6(N-3)(12)(dmeen)(2)(H2O)(2)](n) (2), Cu-6(N-3)(12)(N,N'-dmen)(2)](n) (3), and Cu-6(N-3)(12)(hmpz)(2)](n) (4) aem = 4-(2-aminoethyl)morpholine; dmeen = N,N-dimethyl-N'-ethylethylenediamine; N,N'-dmen = N,N'-dimethylethylenediamine and hmpz = homopiperazine] have been synthesized by using 0.33 mol equiv of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O/CuCl2 center dot 2H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-6(II) building blocks. But the overall structures of these complexes vary widely in dimensionality. While 1 is three-dimensional (3D) in nature, 2 and 3 have a two-dimensional (2D) arrangement (with different connectivity) and 4 has a one-dimensional (1D) structure. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all the four complexes. The experimental susceptibility data have been analyzed by some theoretical model equations.

Oriented films of LaNiO3 and other members of the Lan+1NinO3n+1 series, LaCuO3−δ and Pb(Zr0.52Ti0.48)O3, obtained by nebulized spray pyrolysis

The technique of nebulized spray pyrolysis has been explored to find out whether oriented films of certain important oxides can be produced on single-crystal substrates by this relatively gentle method. Starting with acetylacetonate precursors, oriented films of metallic LaNiO3 containing nearly spherical grains (30 nm) have been obtained. Films of near-stoichiometric La4Ni3O10 and La3Ni2O7 showing metallic conductivity have been obtained by this method. This is indeed gratifying since it is difficult to prepare monophasic and stoichiometric bulk samples of these materials. Films of La2NiO4 show the expected semiconducting behavior. In the La-Cu-O system, starting with acetylacetonates, we have obtained films mainly comprising semiconducting La2Cu2O5, which is generally difficult to prepare in bulk form. More interestingly, nebulized spray pyrolysis gives excellent stoichiometric films of Pb(Zr0.52Ti0.48)O-3 consisting of nearly spherical grains (30 nm) which show ferroelectric behavior. The present investigation demonstrates that nebulized spray pyrolysis provides a useful and desirable route to deposite oriented films of complex oxide materials on single-crystal substrates.

Synthesis, Structures, and Magnetic Behavior of a Series of Copper(II) Azide Polymers of Cu-4 Building Clusters and Isolation of a New Hemiaminal Ether as the Metal Complex

Four new neutral copper azido polymers, Cu-4(N-3)(8)(L-1)(2)](n) (1), Cu-4(N-3)(8)(L-2)(2)](n) (2), Cu-4(N-3)(8)(L-3)(2)](n) (3), and Cu-9(N-3)(18)(L-4)(4)](n) (4) L1-4 are formed in situ by reacting pyridine-2-carboxaldehyde with 22-(methylamino)ethyl]pyridine (mapy, L-1), N,N-dimethylethylenediamine (N,N-dmen, L-2), N,N-diethylethylenediamine (N,N-deen, L-3), and N,N,2,2-tetramethylpropanediamine (N,N,2,2-tmpn, L-4)], have been synthesized by using 0.5 mol equiv of the chelating tridentate ligands with Cu-(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single-crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-4(II) building blocks. The overall structure of 3 is two-dimensional, while the other three complexes are one-dimensional in nature. Complex 1 represents a unique example containing hemiaminal ether arrested by copper(R). Complexes 1 and 2 have a rare bridging azido pathway: both end-on and end-to-end bridging azides between a pair of Cu-II centers. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all four complexes. Density functional theory calculations (B3LYP functional) have been performed on complexes 1-3 to provide a qualitative theoretical interpretation of their overall ferromagnetic behavior.

A[Bi3Ti4O13] and A[Bi3PbTi5O16] (A = K, Cs): New n=4 and n=5 members of the layered perovskite series, A[A ' n-1B nO3n+1], and their hydrates

We describe the synthesis and structural characterization of new layered bismuth titanates, A[Bi3Ti4O13] and A[Bi3PbTi5O16]for A = K, Cs, corresponding to n = 4 and 5 members of the Dion-Jacobson series of layered perovskites of the general formula, A[A'n-1BnO3n+1]. These materials have been prepared by solid state reaction of the constituents containing excess alkali, which is required to suppress the formation of competitive Aurivillius phases. Unlike the isostructural niobates and niobium titanates of the same series, the new phases reported here are spontaneously hydrated-a feature which could make them potentially useful as photocatalysts for water splitting reaction. On hydration of the potassium compounds, the c axis expands by ca. 2 Angstrom and loses its doubling [for example, the tetragonal lattice parameters of K[Bi3Ti4O13] and its dihydrate are respectively a = 3900(1)Angstrom c 37.57(2) Angstrom; a 3.885(1) Angstrom, c = 20.82(4) Angstrom]; surprisingly, the cesium analogues do not show a similar change on hydration.

Homo- or Heterosynthon? A Crystallographic Study on a Series of New Cocrystals Derived from Pyrazinecarboxamide and Various Carboxylic Acids Equipped with Additional Hydrogen Bonding Sites

Four new cocrystals of a well studied active pharmaceutical ingredient (API), namely, pyrazinecarboxamide (PZA), with various monocarboxylic acids equipped with additional hydrogen bonding sites such as vanillic acid (VA), gallic acid (GA), 1-hydroxy-2-naphthoic acid (1HNA), and indole-2-carboxylic acid (I2CA) have been successfully prepared and characterized by FTIR, H-1 NMR, differential scanning calorimetry (DSC), and single crystal and powder X-ray diffraction (SXRD and PXRD, respectively) techniques. In the majority of the cases, preferential occurrence amide amide and acid acid homosynthons has been observed. Since the heterosynthon is energetically preferred to homosynthon, such unusual occurrence of homosynthon in these cocrystals is intriguing.

Taylor series expansion based multidimensional image reconstruction for confocal and 4pi microscopy

We propose and experimentally demonstrate a three-dimensional (3D) image reconstruction methodology based on Taylor series approximation (TSA) in a Bayesian image reconstruction formulation. TSA incorporates the requirement of analyticity in the image domain, and acts as a finite impulse response filter. This technique is validated on images obtained from widefield, confocal laser scanning fluorescence microscopy and two-photon excited 4pi (2PE-4pi) fluorescence microscopy. Studies on simulated 3D objects, mitochondria-tagged yeast cells (labeled with Mitotracker Orange) and mitochondrial networks (tagged with Green fluorescent protein) show a signal-to-background improvement of 40% and resolution enhancement from 360 to 240 nm. This technique can easily be extended to other imaging modalities (single plane illumination microscopy (SPIM), individual molecule localization SPIM, stimulated emission depletion microscopy and its variants).