Synthesis and complexation studies of intra annularly linked bicyclic cyclophanes

The cyclophanes derived from 2,6-bis(chloromethyl)benzoquinone and suitable dithiols were reduced with sodium dithionate and then further coupled with various dibromides to give intra annularly linked bicyclic cyclophanes, which forms charge transfer complexes with TCNQ and TCNE.     

Critical phenomena in FINEMET alloy

The Fe_73.5Cu₁Nb₃Si_13.5B₉ FINEMET alloy has been prepared by the rapid solidification technique. The critical behaviour of this alloy in the amorphous as well as in its nanocrystalline states has been studied near their respective Curie temperatures. From the values of the critical exponents one can conclude that the alloy behaves like a 3D Heisenberg ferromagnet in the amorphous and nanocrystalline states. But there exists a slight increase in the value of β for the alloy annealed at 823 K (the nanocrystalline state) as observed in most of the amorphous alloys.     

Synthesis and photoluminescence properties of some novel fluorenophanes

Fluorenophanes derived from 2,7-bis-(bromomethyl)-9,9′-diheptyl-9H-fluorene and various diols exhibit excellent photoluminescence properties.     

PIV studies of large scale structures in the near field of small aspect ratio elliptic Jets

The near flow field of small aspect ratio elliptic turbulent free jets (issuing from nozzle and orifice) was experimentally studied using a 2D PIV Two point velocity correla tions in these jets revealed the extent and orientation of the large scale structures in th e major and minor planes. The spatial filtering of the instantaneous velocity field using Gaussian convolution kernel shows that while a single large vortex ring circumscribing the jet seems to be present at the exit of nozzle, the orifice jet exhibited a number of smaller vortex ring pairs close to jet exit. The smaller length scale observed in the case of the orifice jet is rep resentative of the smaller azimuthal vor tex rings that generate axial vortex field as they are convected. This results in the axis-switching in th e case of orifice jet and may have a mechanism differ ent from the self induction process as observed in the case of contoured nozzle jet flow.     

Modeling of the microwave drying process of aqueous dielectrics

We propose a thermodynamic framework for describing the microwave drying process of aqueous dielectrics based on Maxwell-Lorentz Field equations and mixture theory. Several issues are discussed such as the form of entropy equation; the constitutive relations for the macroscopic electric polarization vectors, Cauchy stresses, heat fluxes, internal momentum supplies, etc., for each component of the mixture: porous solid, water and gas in different regions; and the interfacial jump conditions between different regions in the mixture. A brief examination of the status of material frame indifference within the context of our framework is presented.     

Subtilisin catalysis of substrate anchored in cyclodextrin

The N-benzoyl-l-tyrosine ethyl ester (BTEE) anchored in cyclodextrin (β and β-methyl CD) serves as an excellent substrate for subtilisin Carlsberg catalysis. The rate of hydrolysis was found to be approximately twofold higher than that of the methanolic substrate. The K_mapp and V_max values for the CD anchored substrates were significantly higher than the methanol-solubilized BTEE.     

Modeling high-pressure densities at wide temperature range with volume scaling: Cyclohexane + n-hexadecane mixtures

High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters.     

Halogenbenzaldehyde, 3. Mitt.

Zusammenfassung Mittels der Konversion aromatischer Amine in die entsprechenden Benzaldehyde, einer Methode, die vonBeech entwickelt und von uns auf Haloaniline erweitert wurde, werden in einfacher, eleganter Weise zwei Halogenbenzaldehyde dargestellt.2. Mitt.:S. D. Jolad undS. Rajagopal, Naturwiss.48, 645 (1961).     

Transport of excitation energy in a doped molecular aggregate. III. numerical investigation of exciton hopping with various exciton-depleting processes

A brute-force numerical investigation has been carried out on the hopping of excitons in a three-dimensional molecular aggregate. Possibilities of vibronic decay, rapid chemical reactions of saturated species, radiative decay of overpopulated molecules, and cooperative chemical reactions involving saturated exciton populations on traps of two different types have been considered. Investigation have been performed with two types of initial distribution of excitons—facial and random—and for 10,000 or, sometimes, for 20,000 time steps each of duration 1ps. Several interesting observations have been made from this computer experiment: (1) The total number of occurrences of fast reactions depends upon the initial distribution of excitons. (2) It decreases if other exciton depleting processes are at work. (3) It also depends on the pattern of placement of traps. (4) The location of impurities also affects the rate of occurrence of these reactions. Thus, more reactions occur when the excitons are initially concentrated on one face and traps are suitably located on the path of flow of these excitons. A random initial distribution tends to equilibrate the excitons quickly over all the lattice points, thus giving rise to fewer reactions. (5) The number of reactions need not necessarily increase with the number of reaction centers; in fact, it decreases as more centers are added when the supply of excitons is severely limited. (6) A Complicated dynamics results when different types of additional processes, viz., enhanced fluorescence, radiative emissions, and cooperative chemical reactions are simultaneously allowed. The cooperative process has been clearly found to dominate. A first-order rate constant of about 10⁸ s-¹ has been calculated for the occurrence of the cooperative process. This rate is affected when other nonconserving processes are switched on. Observations (1), (4), and (5) are the most important conclusions of our work. They lie outside the scope of traditional models such as the random walk model, the diffusion model, and the lattice model for the migration of excitons in a molecular aggregate. © 1993 John Wiley & Sons, Inc.