Dual amplified spontaneous emission as evidence for superexciplex from the dye LD473

Pulsed laser excitation of certain laser dye solutions prepares the sample molecules in a condition, unavailable under steady state lamp excitation. Excited molecules in large concentration obtainable under intense pulse laser pumping appear to undergo superexciplex interaction in which two excited molecules form an association with a solvent molecule acting as a link. This paper shows some of the important features of such superexciplexes with LD473 dye molecule as a reference.     

Palladium-catalyzed [2 + 2 + 2] cocyclotrimerization of benzynes with bicyclic alkenes: an efficient route to anellated 9,10-dihydrophenanthrene derivatives and polyaromatic compounds

An efficient method for the cocyclotrimerization of bicyclic alkenes and benzynes catalyzed by palladium phosphine complexes to give the corresponding norbornane anellated 9,10-dihydrophenanthrene derivatives is described. Bicyclic alkenes 1a-i undergo [2 + 2 + 2] cocyclotrimerization with benzynes generated from precursors 2a-d [2-(trimethylsilyl)phenyl triflate (2a), 4,5-dimethyl-2-(trimethylsilyl)phenyl triflate (2b), 6-(trimethylsilyl)-2,3-dihydro-1H-5-indenyl triflate (2c), 4-methyl-2-(trimethylsilyl)phenyl triflate (2d)] in the presence of PdCl(2)(PPh(3))(2) in acetonitrile at ambient temperature to yield anellated 9,10-dihydrophenanthrene products 3a-r in moderate to excellent yields. The [2 + 2 + 2] cocyclotrimerization products from oxa- and azabicyclic alkenes can be applied for the synthesis of polyaromatics, substituted benzo[b]triphenylenes (8a-f), via a simple Lewis acid mediated deoxyaromatization in good yields. In addition the [2 + 2 + 2] products undergo retro Diels-Alder reaction readily, providing a new method for the synthesis of substituted phenanthrenes and for generating isobenzofurans. A plausible mechanism is proposed to account for the catalytic [2 + 2 + 2] cycloaddition reaction.     

Reactions in the presence of organic phosphites,II: Low-temperature amidatior in solvent

Polyamides and related model compounds were prepared from carboxy acids and primary amines by reacting them with triphenylphosphite in an appropriate solvent at 100°C. The reactions proceeded in the absence of organic base but were accelerated by the addition of bases such as pyridine. Nevertheless, even the powerful combination of ¹³C and ³¹P NMR failed to indicate the presence of pyridinium phosphite in the reaction mixture. In the reaction of a primary amine and carboxyl groups a detectable amount of the diphenoxy aminophosphine intermediate was observed. The end products are the amides, phenol, and diphenyl phosphite. When primary amine was not present a slow formation of a phenyl ester of the carboxylic acid was evident. All the intermediate species and the end products were formed with or without added pyridine. A mixed anhydride of carboxylic acid and phosphite was never seen. The results in this article are fundamentally the same as those in the companion article (I) for which the data were obtained at 280°C in the absence of solvent and base. However, because the reaction went quickly to completion at 280°C, the diphenoxy aminophosphine intermediate was not observed. A mechanism for the amidation in which the diphenoxy aminophosphine is an initial reaction intermediate is proposed. This species reacts with the carboxylic acid through an intramolecular substitution to give an amide. This mechanism may be valid for the high-temperature reactions as well. Several minor unclear points are indicated.     

A highly regio- and stereoselective nickel-catalyzed ring-opening reaction of alkyl- and allylzirconium reagents to 7-oxabenzonorbornadienes

[Reaction: see text]. An efficient method for the synthesis of cis-2-alkyl- or allyl-1,2-dihydronaphthalenes via a nickel-catalyzed highly regio- and stereoselective ring-opening addition of alkyl- or allylzirconium reagents to 7-oxabenzonorbornadienes is described. Treatment of 7-oxabenzonorbornadienes 1a-c with various alkylzirconium reagents 2a-j (Cp2ZrClCH2CH2R: R = tert-butyl, n-butyl, n-pentyl, -(CH2)3CH=C(CH3)2, -SiMe3, -CH2SiMe3, -(CH2)3Br, cyclopentyl, cyclohexyl, and benzyl) in the presence of NiBr2(dppe) and Zn powder in dry THF at 50 degrees C afforded the corresponding cis-2-alkyl-1,2-dihydronaphthalene derivatives 3a-m in good yields. In addition, allyl zirconium reagents 4a-c also underwent ring-opening reactions with 1a and 1c to give 5a-d in very good yields. The alkylative ring-opening products from 7-oxabenzonorbornadiene can be further converted to naphthalene derivatives 6a-c, via an acid-mediated dehydration, in good to excellent yields. A possible mechanism for the present catalytic reaction was proposed.     

The Genus Cetraria s. str.—A Review of Its Botany,Phytochemistry, Traditional Uses and Pharmacology

The genus Cetraria s. str. (Parmeliaceae family, Cetrarioid clade) consists of 15 species of mostly erect brown or greenish yellow fruticose or subfoliose thallus. These Cetraria species have a cosmopolitan distribution, being primarily located in the Northern Hemisphere, in North America and in the Eurasia area. Phytochemical analysis has demonstrated the presence of dibenzofuran derivatives (usnic acid), depsidones (fumarprotocetraric and protocetraric acids) and fatty acids (lichesterinic and protolichesterinic acids). The species of Cetraria, and more particularly Cetraria islandica, has been widely employed in folk medicine for the treatment of digestive and respiratory diseases as decoctions, tinctures, aqueous extract, and infusions. Moreover, Cetraria islandica has had an important nutritional and cosmetic value. These traditional uses have been validated in in vitro and in vivo pharmacological studies. Additionally, new therapeutic activities are being investigated, such as antioxidant, immunomodulatory, cytotoxic, genotoxic and antigenotoxic. Among all Cetraria species, the most investigated by far has been Cetraria islandica, followed by Cetraria pinastri and Cetraria aculeata. The aim of the current review is to update all the knowledge about the genus Cetraria covering aspects that include taxonomy and phylogeny, morphology and distribution, ecological and environmental interest, phytochemistry, traditional uses and pharmacological properties.     

Synthesis of novel hierarchical ZSM-5 monoliths and their application in trichloroethylene removal

A self-supporting ZSM-5 monolith with a hierarchical porosity was prepared using polyurethane foam (PUF) as a structural template and a hydrothermal synthesis procedure. The synthesized monolith was characterized and investigated towards the adsorption and catalytic oxidation of trichloroethylene (TCE). Adsorption of TCE was studied gravimetrically and oxidation of TCE was studied using a vapor-phase down-flow reactor. Monolithic ZSM-5 displayed good sorption properties and completely oxidized TCE. Conversion levels of 50% and 90% were achieved at reduced temperatures (by ~50 ℃) when compared with the conversion temperatures obtained from the powder counterparts. Besides the activity of the monolith towards TCE adsorption and oxidation, it was stable and enhanced diffusion, thereby reducing pressure drops to a great extent owing to its hierarchical porous nature.     

Design and Activity of Novel Oxadiazole Based Compounds That Target Poly(ADP-ribose) Polymerase

Novel PARP inhibitors with selective mode-of-action have been approved for clinical use. Herein, oxadiazole based ligands that are predicted to target PARP-1 have been synthesized and screened for the loss of cell viability in mammary carcinoma cells, wherein seven compounds were observed to possess significant IC₅₀ values in the range of 1.4 to 25 µM. Furthermore, compound 5u, inhibited the viability of MCF-7 cells with an IC₅₀ value of 1.4µM, when compared to Olaparib (IC₅₀ = 3.2 µM). Compound 5s also decreased cell viability in MCF-7 and MDA-MB-231 cells with IC₅₀ values of 15.3 and 19.2 µM, respectively. Treatment of MCF-7 cells with compounds 5u and 5s produced PARP cleavage, H2AX phosphorylation and CASPASE-3 activation comparable to that observed with Olaparib. Compounds 5u and 5s also decreased foci-formation and 3D Matrigel growth of MCF-7 cells equivalent to or greater than that observed with Olaparib. Finally, in silico analysis demonstrated binding of compound 5s towardsthe catalytic site of PARP-1, indicating that these novel oxadiazoles synthesized herein may serve as exemplars for the development of new therapeutics in cancer.     

Direct evidence for an intrinsic square vortex lattice in the overdoped high- T(c) superconductor La(1.83)Sr(0.17)CuO(4+delta)

We report here the first direct observations of a well ordered vortex lattice in the bulk of a La(2-x)Sr(x)CuO(4+delta) single crystal (slightly overdoped, x = 0.17). Our small angle neutron scattering investigation of the mixed phase reveals a crossover from triangular to square coordination with increasing magnetic field. The existence of an intrinsic square vortex lattice has never been observed in high-temperature superconductors and is indicative of the coupling of the vortex lattice to a source of anisotropy, such as those provided by a d-wave order parameter or the presence of stripes.     

Molecular contrast in optical coherence tomography by use of a pump-probe technique

We describe a novel technique for contrast enhancement in optical coherence tomography (OCT) that makes possible molecular-specific imaging for what is believed to be the first time. A pump-probe technique is employed in which a pulsed pump laser is tuned to ground-state absorption in a molecule of interest. The location of the target molecule population is derived from the resulting transient absorption of OCT sample-arm light acting as probe light. A signal processing technique for three-dimensional localization of the transient absorption signal is described, and preliminary results exhibiting OCT contrast from methylene blue dye in multilayer and scattering phantoms are presented.     

Highly regio- and chemoselective palladium-catalyzed three-component assembly of arylethylidene malononitriles,allylic chlorides,and allenylstannanes: a novel route to 1,7-enyne derivatives

[reaction: see text] An efficient method for the synthesis of 1,7-enyne derivatives via a palladium-catalyzed three-component assembly of arylethylidene malononitriles, allylic chlorides, and allenylstannanes is described.