A study of 1O2 production by immobilized sensitizer outside the solution. Measurement of 1O2 generation

Abstract— Recently, a new technique of ¹O₂ generation has been described by Midden and Wang. The sensitizer is immobilized on silica gel particles which are attached on one surface of a glass plate which is placed, sensitizer-side down, above a solution leaving a small air space between the sensitizer and the solution. Applying the principle of the technique, i.e. generation of ¹O₂ in the gas phase above the solution, we first improved the long-term stability of the dye (rose bengal) by using double stock transparent tape instead of rubber cement. Under these conditions, although the initial rate of production was higher in rubber cement, the rate of production reached a plateau after 30 min, whereas with double stick transparent tape, the rate of generation was linear up to 100 min. This result was explained by the fact that silica glass beads are embedded in the cement which could lead to the bleaching reaction of the dye. Different reactions have been investigated, the bleaching of N,N-dimethyl-4-nitrosoaniline (RNO) in the presence of imidazole, destruction of anthracenedipropionic acid, formation of a stable nitroxide from a sterically hindered secondary amine and the influence of pH on the nitroxide yield. The yield was measured to be 5 × 10¹² molecules of singlet oxygen produced per second per cm² from the surface of the plate using the RNO bleaching reaction. This method of generating ¹O₂ also seems promising for studying the killing of mammalian cells by ¹O₂ as the sole damaging species.     

Synthesis and applications of cyano‐vinylene‐based polymers containing cyclopentadithiophene and dithienosilole units for photovoltaic cells

Two β‐cyano‐thiophenevinylene‐based polymers containing cyclopentadithiophene ( CPDT‐CN ) and dithienosilole ( DTS‐CN ) units were synthesized via Stille coupling reaction with Pd(PPh₃)₄ as a catalyst. The effects of the bridged atoms (C and Si) and cyano‐vinylene groups on their thermal, optical, electrochemical, charge transporting, and photovoltaic properties were investigated. Both polymers possessed the highest occupied molecular orbital (HOMO) levels of about ?5.30 eV and the lowest unoccupied molecular orbital (LUMO) levels of about ?3.60 eV, and covered broad absorption ranges with narrow optical band gaps (ca. 1.6 eV). The bulk heterojunction polymer solar cell (PSC) devices containing an active layer of electron‐donor polymers ( CPDT‐CN and DTS‐CN ) blended with an electron‐acceptor, that is, [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) or [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM), in different weight ratios were explored under 100 mW/cm² of AM 1.5 white‐light illumination. The PSC device based on DTS‐CN: PC₇₁BM (1:2 w/w) exhibited a best power conversion efficiency (PCE) value of 2.25% with V_oc = 0.74 V, J_sc = 8.39 mA/cm², and FF = 0.36. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Base dependent pyrrolidine ring pucker in aep-PNA monomers: NMR and PSEUROT analysis

The aep-PNA is a chiral and cyclic PNA analogue, which has a stronger and base dependent binding affinity with complementary DNA. To understand the base dependent properties at monomer level, the structural studies of aep-PNA-(T/C/A) monomers have been carried out focussing on the conformational analysis of pyrrolidine ring pucker in aep-PNA by ¹H NMR and the coupling constant data fitted into PSEUROT software. The results indicate that the type of pyrrolidine pucker depends on the electronic nature of substituent, implying the effect of pyrimidine or purine substituents in determining the ring pucker in monomers. This may consequently influence the aep-PNA oligomer conformation. Since pyrrolidine nucleic acids have emerged as an important class of PNA analogues, present results may have importance for their future development.     

Studies in spiroheterocycles,Part XV. Investigation of the reaction of 3-(2-oxocycloalkylidene)-indol-2-ones with thiourea and urea derivatives

The reaction of 3-(2-oxocycloalkylidene)indol-2-one 1 with thiourea and urea derivatives has been investigated. Reaction of 1 with thiourea and urea in ethanolic potassium hydroxide media leads to the formation of spiro-2-indolinones 2a-f in 40–50% yield and a novel tetracyclic ring system 4,5-cycloalkyl-1,3-diazepino-[4,5-b]indole-2-thione/one 3a-f in 30–35% yield. 3-(2-Oxocyclopentylidene)indol-2-one afforded 5′,6′-cyclopenta-2′-thioxo/ oxospiro[3H-indole-3,4′(3′H)pyrimidin]-2(1H)-ones 2a,b and 3-(2-oxocyclohexylidene)indol-2-one gave 2′,4′a,5′,6′,7′,8′- hexahydro-2′-thioxo/oxospiro[3H-indole-3,4′ (3′H)-quinazolin]-2(1H)-ones 2c-f . Under exactly similar conditions, reaction of 1 with fluorinated phenylthiourea/cyclohexylthiourea/phenylurea gave exclusively spiro products 2g-1 in 60–75% yield. The products have been characterized by elemental analyses, ir pmr. ¹⁹F nmr and mass spectral studies.     

Synthesis and biological evaluation of some new class of benzothiazole–pyrazole ligands containing arene ruthenium,rhodium and iridium complexes

Transition Metal Chemistry - Metal complexes 1–9 have been synthesized by reacting the benzothiazole–pyrazole derivative ligands (L1, L2 and L3) with the metal precursors of ruthenium...     

Reusable Nano-Zirconia-Catalyzed Synthesis of Benzimidazoles and Their Antibacterial and Antifungal Activities

In this article, a zirconia-based nano-catalyst (Nano-ZrO₂), with intermolecular C-N bond formation for the synthesis of various benzimidazole-fused heterocycles in a concise method is reported. The robustness of this reaction is demonstrated by the synthesis of a series of benzimidazole drugs in a one-pot method. All synthesized materials were characterized using ¹HNMR, ¹³CNMR, and LC-MS spectroscopy as well as microanalysis data. Furthermore, the synthesis of nano-ZrO₂ was processed using a standard hydrothermal technique in pure form. The crystal structure of nano-ZrO₂ and phase purity were studied, and the crystallite size was calculated from XRD analysis using the Debye–Scherrer equation. Furthermore, the antimicrobial activity of the synthesized benzimidazole drugs was evaluated in terms of Gram-positive, Gram-negative, and antifungal activity, and the results were satisfactory.     

Thermal behaviour of bisitaconimide and reactive diluent blends

Thermal behaviour of blends based on N,N'-bis(4-itaconimidophenyl) ether (IE) and 4,4'-bis(4-allyl-2-methoxyphenoxy) benzophenone (R₁) or 4,4'-bis(2-allylphenoxy) benzophenone (R₂) are described in this paper. The reactive diluent content was varied from 5-50% (mass/mass) in these blends. A decrease in the melting point and exothermic peak temperature was observed with increasing mass percent of reactive diluent. Thermal stability of blends was affected at high mass percentage of reactive diluents. This revised version was published online in August 2006 with corrections to the Cover Date.     

Dichloroborane-dioxane: an exceptional reagent for the preparation of alkenyl- and alkylboronic acids

Terminal alkynes and alkenes were conveniently hydroborated to the corresponding alkenyl- and alkyldichloroboranes using dichloroborane-dioxane in dichloromethane. These dichloroboranes were hydrolyzed by water to the corresponding alkenyl- and alkylboronic acids in moderate to good yields. With terminal alkenes and alkynes boron was predominantly attached to terminal carbon. Alkynes gave exclusively trans-vinylboronic acids.     

Synthesis of the southern furan segment of furanocembranoids

Abstract

A convergent synthesis of the southern furan segment of novel furanocembranoids from Croton oblongifolius has been accomplished involving silver-catalyzed cyclization of alkynyl diol as the key step towards 2, 5-disubstituted furan ring formation.     

Synthesis of Dihydropyridine Derivatives under Eco‐friendly Approach and Investigation of Cytotoxic Activity

In an effort for development of innovative biologically active agents, a sequence of 1,4‐dihydropyridine analogues was synthesized through the green synthetic method. In addition, all compounds were evaluated for their cytotoxic activities against three human cancer cell lines and mouse melanoma and figured out the most active compounds. Besides, promoter reusability, easy handling of the chemical reagent, simple reaction process, time minimization, ethanol–water solvent compatibility, and cost reduction reagent are key tools for this fruitful path. Thus, these examinations recommended that dihydropyridine and their derivatives are motivating moieties for the discovery of new anticancer drugs.