Partial rotation of the isopropyl group in the solid state: single-crystal-to-single-crystal phase transformation in a carvacrol derivative

A hitherto unseen rotation of the isopropyl group in the solid state, predicted to be forbidden based on theoretical investigations, is reported. This C-C rotation observed during the temperature dependent single-crystal-to-single-crystal transformation is attributed to the concomitant changes in molecular structure and intermolecular packing.

Enantio sensing property of helicin, the derivative of a natural product: Discrimination of amines and amino alcohols

The chiral sensing property of helicin (the derivative of natural product obtained by partial oxidation of salicin, extracted from willow tree (Salix helix)) is reported. The use of helicin as a chiral derivatizing agent for the discrimination of amines and amino alcohols is convincingly established using H-1 NMR spectroscopy. The large chemical shift separation achieved between the discriminated peaks facilitated the accurate quantification of enantiomeric composition. The consistent trend observed in the shifting of imine proton peak (Delta delta) of helicin in all the derivatized molecules might aid the determination of spatial configuration. (C) 2015 Elsevier B.V. All rights reserved.

A novel benzimidazole derivative binds to the DNA minor groove and induces apoptosis in leukemic cells

DNA minor groove binders are an important class of chemotherapeutic agents. These small molecule inhibitors interfere with various cellular processes like DNA replication and transcription. Several benzimidazole derivatives showed affinity towards the DNA minor groove. In this study we show the synthesis and biological studies of a novel benzimidazole derivative (MH1), that inhibits topoisomerase II activity and in vitro transcription. UV-visible and fluorescence spectroscopic methods in conjunction with Hoechst displacement assay demonstrate that MH1 binds to DNA at the minor groove. Cytotoxic studies showed that leukemic cells are more sensitive to MH1 compared to cancer cells of epithelial origin. Further, we find that MH1 treatment leads to cell cycle arrest at G2/M, at early time points in Molt4 cells. Finally multiple cellular assays demonstrate that MH1 treatment leads to reduction in MMP, induction of apoptosis by activating CASPASE 9 and CASPASE 3. Thus our study shows MH1, a novel DNA minor groove binder, induces cytotoxicity efficiently in leukemic cells by activating the intrinsic pathway of apoptosis.

A Deep-Blue Electroluminescent Device Based on a Coumarin Derivative

The design and synthesis is reported of 7-(9H-carbazol-9-yl)-4-methylcoumarin (Cz-Cm), comprising a carbazole donor moiety and a 4-methylcoumarin acceptor unit, for use in a blue organic light-emitting diode. A detailed solid state, theoretical and spectroscopic study was performed to understand the structure-property relationships. The material exhibits deep-blue emission and high photoluminescence quantum yield both in solution and in a doped matrix. A deep-blue electroluminescence emission at 430nm, a maximum brightness of 292cdm(-2) and an external quantum efficiency of 0.4% was achieved with a device configured as follows: ITO/NPD (30nm)/TCTA (20nm)/CzSi(10nm)/10wt% Cz-Cm:DPEPO (10nm)/TPBI (30nm)/LiF (1nm)/Al ITO=indium tin oxide, NPD=N,N-di(1-naphthyl)-N,N-diphenyl-(1,1-biphenyl)-4,4-diamine, TCTA=tris(4-carbazoyl-9-ylphenyl)amine, CzSi=9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole, DPEPO=bis2-(diphenylphosphino)phenyl]ether oxide, TPBI=1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene].

Uniform stability of a particle approximation of the optimal filter derivative

Sequential Monte Carlo methods, also known as particle methods, are a widely used set of computational tools for inference in non-linear non-Gaussian state-space models. In many applications it may be necessary to compute the sensitivity, or derivative, of the optimal filter with respect to the static parameters of the state-space model; for instance, in order to obtain maximum likelihood model parameters of interest, or to compute the optimal controller in an optimal control problem. In Poyiadjis et al. [2011] an original particle algorithm to compute the filter derivative was proposed and it was shown using numerical examples that the particle estimate was numerically stable in the sense that it did not deteriorate over time. In this paper we substantiate this claim with a detailed theoretical study. Lp bounds and a central limit theorem for this particle approximation of the filter derivative are presented. It is further shown that under mixing conditions these Lp bounds and the asymptotic variance characterized by the central limit theorem are uniformly bounded with respect to the time index. We demon- strate the performance predicted by theory with several numerical examples. We also use the particle approximation of the filter derivative to perform online maximum likelihood parameter estimation for a stochastic volatility model.

Preparation and characterization of an intramolecular electron transfer in a pentaammineruthenium derivative of Candida krisei cytochrome c

A semisynthetic binuclear metalloprotein has been prepared by appending the pentaammineruthenium moiety to histidine 39 of the cytochrome c from the yeast Candida krusei. The site of ruthenium binding was identified by peptide mapping. Spectroscopic and electrochemical properties of the derivative indicate the protein conformation is unperturbed by the modification. A preliminary (minimum) rate constant of 170s^(-1) has been determined for the intramolecular electron transfer from ruthenium(II) to iron(III), which occurs over a distance of at least 13Å (barring major conformational changes). Electrochemical studies indicate that this reaction should proceed with a driving force of ~170mV. The rate constant is an order of magnitude faster than that observed in horse heart cytochrome c for intramolecular electron transfer from pentaammineruthenium(II)(histidine 33) to iron(III) (over a similar distance, and with a similar driving force), suggesting a medium or orientation effect makes the Candida intramolecular electron transfer more favorable.

Measurement of two-photon excitation cross-section of a new symmetric-type fluorene derivative

A new dye, 2,7-bis(4-methoxystyryl)-9,9-bis(2-ethylhexyl)-9H-fluorene, has been synthesized, which is a D-pi-D symmetrical-type fluorene derivative. The two-photon absorption (TPA) of this new dye has been experimentally studied by comparable two-photon-induced fluorescence method. This new dye has a TPA cross-section of 84 x 10(-50) cm(4) s/photon at 790 nm/13 fs. (c) 2004 Elsevier GmbH. All rights reserved.

Weighted least-squares phase unwrapping algorithm based on derivative variance correlation map

Among different phase unwrapping approaches, the weighted least-squares minimization methods are gaining attention. In these algorithms, weighting coefficient is generated from a quality map. The intrinsic drawbacks of existing quality maps constrain the application of these algorithms. They often fail to handle wrapped phase data contains error sources, such as phase discontinuities, noise and undersampling. In order to deal with those intractable wrapped phase data, a new weighted least-squares phase unwrapping algorithm based on derivative variance correlation map is proposed. In the algorithm, derivative variance correlation map, a novel quality map, can truly reflect wrapped phase quality, ensuring a more reliable unwrapped result. The definition of the derivative variance correlation map and the principle of the proposed algorithm are present in detail. The performance of the new algorithm has been tested by use of a simulated spherical surface wrapped data and an experimental interferometric synthetic aperture radar (IFSAR) wrapped data. Computer simulation and experimental results have verified that the proposed algorithm can work effectively even when a wrapped phase map contains intractable error sources. (c) 2006 Elsevier GmbH. All rights reserved.

Theoretical investigation on the one- and two-photon absorption properties for a series of symmetrical charge transfer fluorene-phenylene and fluorene-thiophene derivatives

One- and two-photon absorption properties of a series of fluorene derivatives with symmetrical charge transfer D-IT-D and A-IT-A structural motifs have been theoretically investigated with ZINDO/S method. The optimized structures and the characterization of frontier molecular orbitals were obtained by using AMI calculations. Two-photon absorption properties of molecules have been studied using three-state model. The calculation results have shown that fluorene-thiophene derivatives exhibit larger two-photon absorption cross-section as compared with other studied molecules. To illustrate the results, the crucial effects of thiophene ring on fluorenethiophene derivatives and the net charge changes on the pi-conjugated bridges are analyzed theoretically. (c) 2006 Elsevier B.V. All rights reserved.