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151.
Anasuya Mishra Arumugam Thangamani Soumya Chatterjee Francis A. S. Chipem Govindarajan Krishnamoorthy 《Photochemistry and photobiology》2013,89(1):247-252
Photoreaction of trans‐2‐[4′‐(dimethylamino)styryl]benzothiazole (t‐DMASBT) under direct irradiation has been investigated in dioxane, chloroform, methanol and glycerol to understand the mechanism of photoisomerization. Contrary to an earlier report, isomerization takes place in all these solvents including glycerol. The results show that restriction on photoisomerization leads to the increase in fluorescence quantum yield in glycerol. The results are consistent with the theoretically simulated potential energy surface reported earlier using time‐dependent density functional theory (TDDFT) calculations. DFT calculations on cis isomers under isolated condition have suggested that cis‐B conformer is more stable than cis‐A conformer due to hydrogen‐bonding interaction. In the ground state, cis‐DMASBT is predominantly present as cis‐B. The fluorescence spectra of the irradiated t‐DMASBT suggested that photoisomerization follows not the adiabatic path as proposed by Saha et al., but the nonadiabatic path. 相似文献
152.
Phthalocyanine 4 (Pc 4) is a promising photosensitizer currently in clinical trials. Photobiological responses to Pc 4 photodynamic therapy (Pc 4-PDT) have been characterized extensively, but relatively little has been done to evaluate dose metrics for this sensitizer. We describe an irradiation-induced increase in fluorescence in tumor cell monolayers. This increase is due solely to enhanced fluorescence from Pc 4, as confirmed by confocal spectroscopy. In EMT6 cells incubated with 250 nM Pc 4 for 24 h, the maximum increase in fluorescence is approximately 3.7-fold above baseline levels. This increase occurs over a range of fluences, 0.05-0.6 J cm(-2), where clonogenic survival decreases by 3 orders of magnitude. Light scattering measurements performed on similarly treated EMT6 cells in suspension suggested a Pc 4-PDT-mediated mitochondrial swelling of approximately 13% at 0.6 J cm(-2), where fluorescence enhancement saturates under these treatment conditions. Fluorescence imaging and light scattering experiments performed at a five-fold lower Pc 4 incubation concentration revealed a reduced fluorescence enhancement at a five-fold higher fluence, which produced comparable mitochondrial swelling. Taken together, these data suggest that Pc 4 is initially aggregated at high local concentration in mitochondria and that irradiation relaxes the quenching of Pc 4 fluorescence through a mechanism that may involve mitochondrial swelling. 相似文献
153.
Kanoo P Haldar R Cyriac ST Maji TK 《Chemical communications (Cambridge, England)》2011,47(39):11038-11040
Metal mediated in situ C-N coupling between 4,4'-azobipyridine and disodium-trans-glutaconate at room temperature has formed a new multifunctional linker Z-dhpe which subsequently self-assembles with Zn(II) or Cd(II) resulting in a chiral or an achiral metal-organic framework, respectively, depending on its different coordination modes. 相似文献
154.
Soumya Sarkar Syed Masood Husain Dirk Schepmann Roland Fröhlich Bernhard Wünsch 《Tetrahedron》2012,68(12):2687-2695
Microwave assisted condensation of primary amines with keto acids 1a–c provided directly 3,4-disubstituted 1,3-dihydro-3-benzazepin-2-ones 2. Whereas small amine size, such as NH3 afforded high yields of secondary lactams 2a, 2d, and 2g, primary amines with larger substituents in α-position led to lower yields of 2 or even to regioisomeric indanone derivatives 4. However, subsequent alkylation of 2a, 2d, and 2g with various alkyl halides provided the corresponding N-substituted 3-benzazepin-2-ones 2 in good yields. Hydrogenation of 2 followed by BH3 reduction led to 3-benzazepines 9. 3-Benzyl-2-methyl-2,3,4,5-tetrahydro-1H-3-benzazepine (9c) reveals high σ1 affinity and selectivity over σ2 and NMDA receptors. 相似文献
155.
We prove that, under suitable conditions, certain Siegel Poincaré series of exponential type of even integer weight and degree 2 do not vanish identically. We also find estimates for twisted Kloosterman sums and Salié sums in all generality. 相似文献
156.
Mechanism of Redox‐Active Ligand‐Assisted Nitrene‐Group Transfer in a ZrIV Complex: Direct Ligand‐to‐Ligand Charge Transfer Preferred 下载免费PDF全文
Dr. Soumya Ghosh Prof. Dr. Mu‐Hyun Baik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1780-1789
The mechanism of the nitrene‐group transfer reaction from an organic azide to isonitrile catalyzed by a ZrIV d0 complex carrying a redox‐active ligand was studied by using quantum chemical molecular‐modeling methods. The key step of the reaction involves the two‐electron reduction of the azide moiety to release dinitrogen and provide the nitrene fragment, which is subsequently transferred to the isonitrile substrate. The reducing equivalents are supplied by the redox‐active bis(2‐iso‐propylamido‐4‐methoxyphenyl)‐amide ligand. The main focus of this work is on the mechanism of this redox reaction, in particular, two plausible mechanistic scenarios are considered: 1) the metal center may actively participate in the electron‐transfer process by first recruiting the electrons from the redox‐active ligand and becoming formally reduced in the process, followed by a classical metal‐based reduction of the azide reactant. 2) Alternatively, a non‐classical, direct ligand‐to‐ligand charge‐transfer process can be envisioned, in which no appreciable amount of electron density is accumulated at the metal center during the course of the reaction. Our calculations indicate that the non‐classical ligand‐to‐ligand charge‐transfer mechanism is much more favorable energetically. Utilizing a series of carefully constructed putative intermediates, both mechanistic scenarios were compared and contrasted to rationalize the preference for ligand‐to‐ligand charge‐transfer mechanism. 相似文献
157.
Sanjeeva Thunga Soumya Poshala Naveenkumar Anugu Ramaiah Konakanchi Satheesh Vanaparthi Hari Prasad Kokatla 《Tetrahedron letters》2019,60(31):2046-2048
An efficient new Pd(II)-(2-aminonicotinaldehyde)-catalyzed Suzuki-Miyaura coupling of the aryl halides (Br, Cl and I) and organoboronic acids at moderate temperature in water is described. Low catalyst loading, easy accessibility, being an air-stable catalyst, functional group compatibility, and water as the reaction medium are some of the key features of this synthetic method. This protocol is also applicable for gram scale. 相似文献
158.
Soniya Rani Soumya Ranjan Dash Asish Bera Md Nirshad Alam Kumar Vanka Pradip Maity 《Chemical science》2021,12(26):8996
A phosphite mediated stereoretentive C–H alkylation of N-alkylpyridinium salts derived from chiral primary amines was achieved. The reaction proceeds through the activation of the N-alkylpyridinium salt substrate with a nucleophilic phosphite catalyst, followed by a base mediated [1,2] aza-Wittig rearrangement and subsequent catalyst dissociation for an overall N to C-2 alkyl migration. The scope and degree of stereoretention were studied, and both experimental and theoretical investigations were performed to support an unprecedented aza-Wittig rearrangement–rearomatization sequence. A catalytic enantioselective version starting with racemic starting material and chiral phosphite catalyst was also established following our understanding of the stereoretentive process. This method provides efficient access to tertiary and quaternary stereogenic centers in pyridine systems, which are prevalent in drugs, bioactive natural products, chiral ligands, and catalysts. N-Alkylpyridinium salt of chiral amines undergoes phosphite mediated stereoretentive migrations to generate chiral alkylpyridines. The role of phosphite on reactivity and stereoselectivity were examined to achieve a catalytic asymmetric version. 相似文献