A General Method for the Synthesis of 5H‐Benzo[b]‐, Carbazolo[2,3‐b]‐ and Indolo[2,3‐b]carbazole Derivatives via Copper(II) Triflate‐Catalyzed Heteroannulation

A straightforward approach for the construction of 5H‐benzo[b]‐, carbazolo[2,3‐b]‐ and indolo[2,3‐b]carbazole derivatives has been developed by using copper(II) triflate‐catalyzed heteroannulation.     

Gallium(III) triflate: an efficient and a sustainable Lewis acid catalyst for organic synthetic transformations

Green chemical processes play a crucial role in sustainable development, and efficient recyclable catalysts that can be conveniently applied in various chemical reactions are the key elements for the development of sustainable synthetic processes. Many organic transformations rely on Lewis and Br?nsted acid catalysts, and such molecules have been widely studied in organic synthesis. Over the years, researchers have looked for Lewis acid catalysts that provide high selectivity and high turnover frequency but are also stable in aqueous media and recoverable. Since the first preparation of trifluoromethanesulfonic acid by Hazeldine (triflic acid, HOTf), researchers have synthesized and used numerous metal triflates in a variety of organic reactions. Even though the rare earth metal triflates have played a major role in these studies, the majority of rare earth triflates lack one or more of the primary properties of sustainable catalysts: low cost and easy availability of the metals, easy preparation of triflates, aqueous/thermal stability, recyclability, and catalytic efficiency. In this Account, we describe the synthetic applications of Ga(OTf)(3) and its advantages over similar catalysts. Ga(OTf)(3) can be conveniently prepared from gallium metal or gallium chloride in excess of trifluoromethanesulfonic acid (triflic acid) under reflux. Among many Lewis acid catalysts recently studied, Ga(OTf)(3) is water tolerant and soluble and requires very low catalyst loading to drive various acid-catalyzed reactions including Friedel-Crafts alkylation, hydroxyalkylation, and acylation selectively and efficiently. In many reactions Ga(OTf)(3) demonstrated high chemo- and regioselectivity, high yields, excellent stability, and recyclability. We successfully synthesized many biologically active heterocycles and their fluoroanalogs under mild conditions. Many challenging reactions such as the ketonic Strecker reactions proceed efficiently via Ga(OTf)(3) catalysis. Because it is stable in water, this catalyst provides the opportunity to study substrates and develop new synthetic protocols in aqueous media, significantly reducing the production of hazardous waste from organic solvents and toxic catalyst systems.     

Synthesis of Red-Light-Responsive Pheophorbide-a Tryptamine Conjugated Photosensitizers for Photodynamic Therapy

Six methyl pheophorbide-a derivatives were prepared by linking a tryptamine side chain at the C-13 ¹ , C-15 ² and C-17 ³ positions of pheophorbide-a. P repared conjugates were characterized and evaluated for their photocytotoxicity against A549 cells. The conjugate 6 a with strong absorption at 413 nm (Soret band), 663–671 nm (Q bands) and comparable fluorescence quantum yield (0.26) was found to exhibit significant cytotoxicity (659 nM). Molecular integration of pheophorbide-a and tryptamines showed synergistic effects as the most potent conjugate 6 a was identified with enhanced photocytotoxicity when compared to methyl pheophorbide-a. T he conjugate 6 a was smoothly taken up by A549 cells and exhibited intracellular localization predominantly to lysosome in the cytoplasm. Upon photoirradiation 6 a generated singlet oxygen to show potent cytotoxicity toward A549 cells.     

Reverse atom transfer radical polymerization of stearyl methacrylate using 2,2′‐azobisisobutyronitrile as the initiator

The living/controlled radical polymerization of stearyl methacrylate was carried out with a conventional radical initiator (2,2′‐azobisisobutyronitrile) in N,N‐dimethylformamide in the presence of a 2,2′‐bipyridine complex of hexakis(N,N‐dimethylformamide)iron(III) perchlorate. The polymerization mechanism was thought to proceed through a reverse atom transfer radical polymerization. The molecular weights of resulting poly(stearyl methacrylate) increased with conversion, and the resulting molecular weight distributions were quite narrow. The rates of polymerization exhibited first‐order kinetics with respect to the monomer. A probable reaction mechanism for the polymerization system is postulated to explain the observed results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1236–1245, 2002     

Electrochemistry of polyaniline: Study of the pH effect and electrochromism

Polyaniline was electrochemically synthesized from an aqueous medium with various acid electrolytes via potentiodynamic and potentiostatic techniques. The electrochemical synthesis of polyaniline was studied over various substrates, including Pt, Ti, Ni, and SnO₂ coated glass, and in various acid electrolytes. Cyclic voltammograms of electrochemically synthesized polyaniline were studied in HCl in a pH range of 1–4. Probable electrochemistry and chemical changes were deduced that occurred when polyaniline film was electrochemically oxidized and reduced between ?0.2 and 1.0 V versus a Ag/AgCl reference electrode in an acidic electrolyte at pH 1, and three corresponding oxidation and reduction peaks were described instead of two redox peaks (as observed by W. S. Huang, B. D. Humphrey, and A. G. MacDiarmid, J Chem Soc Faraday Trans 1 1986, 82, 2385). The electrochromic property was studied with changes in the chemical states of polyaniline during electrochemical oxidation and reduction. A new viscous electrolyte, aqueous AlCl₃ (pH 2), saturated with AgCl was used for the construction of an electrochromic display device. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 378–385, 2002     

MCM-41-supported Co-Mo catalysts for deep hydrodesulfurization of light cycle oil

Light cycle oil (LCO), a by-product of the fluid catalytic cracking (FCC) process in a petroleum refinery, can be used as a blendstock for the production of diesel and jet fuels. Regulatory and operational issues result in need for new and more active catalysts for the deep hydrodesulfurization (HDS) of diesel feedstocks, such as LCO. This paper reports the activity of a mesoporous molecular sieve MCM-41-supported Co-Mo catalyst in comparison to a commercial γ-alumina (Al₂O₃)-supported Co-Mo catalyst for the desulfurization of a LCO with a sulfur content of 2.19 wt.%. The HDS of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene—polyaromatic sulfur compounds present in LCO—and their relative reactivities in terms of conversion were examined as a function of time on stream in a fixed-bed flow reactor. The MCM-41-supported catalyst demonstrates consistently higher activity for the HDS of the refractory dibenzothiophenic sulfur compounds, particularly 4,6-dimethyldibenzothiophene. The presence of a large concentration of aromatics in LCO appears to inhibit the HDS of the substituted dibenzothiophenes.     

A case study of long-term RO plant operation without chemical pretreatment

Described herein is a case study of long-term reverse osmosis (RO) plant operation without applying chemical pretreatments to the feed water. This project was undertaken with the financial support from the Department of Bio-Technology, New Delhi, and the work was carried out by a research team from Central Salt and Marine Chemicals Research Institute (CSMCRI), Bhavnagar (Gujarat), India. A prototype plant with a 30,000 L/d capacity was designed, manufactured, installed and operated at the village of Mocha-Gorsar, located in the Porbandar district, to provide drinking water. The village was to be developed as a model Bio-Village where other projects related to village problems are also operated by other research institutes. Thin-film composite (TFC) membrane-based RO technology was indigenously developed by the institute for treatment of brackish water and waste water for the first time in India; it was used successfully in this plant, which gave a typical NaCl rejection of about 95%. This is a typical case study of RO plant installation where physical methods of pretreatment such as sand and micron cartridge filters were used; no chemical pretreatment of feed was employed for long-term brackish water desalination study. The idea was to avoid the usage of chemicals, which concentrate in the effluent water, might affect the environment and may not suit the village community. Plant performance during 24 months of continuous operation with respect to variable feed salinity, membrane cleaning and regenerations is discussed.     

A novel layered Li [Li0.12NizMg0.32−zMn0.56]O2 cathode material for lithium-ion batteries

Layered Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ oxide cathodes containing lithium atoms in the transition metal layers were synthesized and characterized using X-ray diffraction (XRD), galvanostatic cycling, and differential scanning calorimetry (DSC). The Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ cathodes deliver a specific discharge capacity of about 190 mAh/g at room temperature and 236 mAh/g at 55 °C when cycled between 2.7 and 4.6 V versus Li/Li⁺. Excellent capacity retention and smooth potential profiles at room and elevated temperatures over extended cycles suggest that this material does not convert into a spinel structure.     

Photocatalytic,magnetic, and electrochemical properties of La doped BiFeO3 nanoparticles

We successfully prepared La_1?xBi_xFeO₃ (L_xB_1?xFO, x?=?0.01–0.1) nanoparticles using a sol-gel technique, and studied their photocatalytic, magnetic, and electrochemical properties. Structural refinement studies of the prepared nanoparticles revealed a gradual structural transition from rhombohedral to orthorhombic. The average grain size was observed to decrease with increasing the concentration of La. The photocatalytic degradation of Rhodamine B (RhB) in the presence of the prepared nanoparticles was studied under visible light irradiation. The L_0.06B_0.94FO nanoparticles showed higher degradation efficiency compared to pure BiFeO₃ (BFO) nanoparticles. Magnetic studies showed that La doping improved the magnetization of BFO due to the reduction in grain size and destruction of cycloid coupling of spins. Higher specific capacitance values were obtained for La doped BFO (LBFO) nanoparticles compared to BFO nanoparticles. A maximum specific capacitance of 219?F?g^?1 was obtained at a current density of 1?A?g^?1 for LBFO nanoparticles.