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31.
A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett
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Perumal Subramaniam Jebamoney Janet Sylvia Jaba Rose Rajasingh Jeevi Esther Rathinakumari 《Journal of Physical Organic Chemistry》2016,29(10):496-504
Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)3]3+ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)3]3+ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H2O which leading to low magnitude of ρ+ compared to high ρ? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
32.
Deena Gladies Raymond Mohanraj Manikandan Alagumuthu Palaniraja Subramaniam Dhivya Bakthavachalam Sivakumar Arumugam Subha Chellam 《Journal of heterocyclic chemistry》2021,58(7):1515-1524
In this study, the antimicrobial effect and DNA gyrase inhibitor potential of vanillin-based pyridyl–substituted fluoro-indolines were evaluated. These compounds are synthesized and established through green-chemistry approaches. The inhibition effect on both DNA gyrase A and B was evaluated in silico and in vitro. Agar well diffusion method–based antimicrobial activity against Gram-ve Pseudomonas aeruginosa (MTCC 424) and Escherichia coli (MTCC 443), Gram+ve Streptococcus pyogenes (MTCC 442) and Staphylococcus aureus (MTCC 96), and a clinical isolate of Candida albicans (Fungi) was evaluated. The cytotoxicity of the compounds was assessed over macrophages using the MTT assay. In the results, the target compounds exhibited a broad-spectrum antimicrobial activity against both bacterial types and fungal. 相似文献
33.
34.
Soliton squeezing in microstructure fiber 总被引:4,自引:0,他引:4
We demonstrate, for the first time to our knowledge, the generation of squeezed light by means of soliton self-phase modulation in microstructure fiber. We observe and characterize the formation of solitons in the microstructure fiber at 1550 nm. A maximum squeezing of 2.7 dB is observed, corresponding to 4.0 dB after correcting for detection losses. The dependence of this quantum-noise reduction on various system parameters is studied in detail. Features of the microstructure fiber can be exploited for generation of low-energy continuous-variable entangled pulses for use in all-fiber teleportation experiments. 相似文献
35.
We present a fiber-based source of polarization-entangled photons that is well suited for quantum communication applications in the 1550 nm band of standard fiber-optic telecommunications. Polarization entanglement is created by pumping a nonlinear-fiber Sagnac interferometer with two time-delayed orthogonally polarized pump pulses and subsequently removing the time distinguishability by passing the parametrically scattered signal and idler photon pairs through a piece of birefringent fiber. Coincidence detection of the signal and idler photons yields biphoton interference with visibility greater than 90%, while no interference is observed in direct detection of either signal or idler photons. All four Bell states can be prepared with our setup and we demonstrate violations of the Clauser-Horne-Shimony-Holt form of Bell's inequality by up to 10 standard deviations of measurement uncertainty. 相似文献
36.
Previous work performed on electron-irradiated Li2O crystals has demonstrated the simultaneous formation of two populations of colloids of metallic lithium, one is associated with oxygen bubbles and a typical size of >10 microm, while the other one consists of nanoclusters in the range of <10 nm. In the present neutron scattering investigation these small colloids are characterized in detail based on a thorough analysis of distortion scattering around Bragg peaks. It is shown that the small lithium colloids are slightly elongated precipitates with typical dimensions of around approximately 5 nm. For the large lithium colloids a well-defined orientation relation with respect to the Li2O matrix has been determined. 相似文献
37.
We demonstrate theoretically and experimentally that secure communication using intermediate-energy (mesoscopic) coherent states is possible. Our scheme is different from previous quantum cryptographic schemes in that a short secret key is explicitly used and in which quantum noise hides both the bit and the key. This encryption scheme allows optical amplification. New avenues are open to secure communications at high speeds in fiber-optic or free-space channels. 相似文献
38.
Misra SK Andronenko SI Rinaldi G Chand P Earle KA Freed JH 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,160(2):131-138
Multifrequency electron paramagnetic resonance studies on the Mn(2+) impurity ion in a mixed single crystal NH(4)Cl(0.9)I(0.1) were carried out at 9.62 (X-band) in the range 120-295 K, at 35.87 (Q-band) at 77 and 295 K, and at 249.9 GHz (far-infrared band) at 253 K. The high-field EPR spectra at 249.9 GHz are well into the high-field limit leading to a considerable simplification of the spectra and their interpretation. Three magnetically inequivalent, but physically equivalent, Mn(2+) ions with their respective magnetic Z-axes oriented along the crystallographic [100], [010], [001] axes were observed. Simultaneous fitting of EPR line positions observed at X-, Q-, and far infra-red bands was performed using a least-squares procedure and matrix diagonalization to estimate accurately the Mn(2+) spin-Hamiltonian parameters. The temperature variation of the linewidth and peak-to-peak intensities of the EPR lines indicate the presence of lambda-transitions in the mixed NH(4)Cl(0.9)I(0.1) crystal at 242 and 228 K consistent with those observed in the pure NH(4)Cl and NH(4)I crystals, respectively. A superposition-model analysis of the spin-Hamiltonian parameters reveals that the local environment of the Mn(2+) ion is considerably reorganized to produce axially symmetric crystal fields about the respective Z-axes of the three magnetically inequivalent ions as a consequence of the vacancy created due to charge-compensation when the divalent Mn(2+) ion substitutes for a monovalent NH(4)(+) ion in the NH(4)Cl(0.9)I(0.1) crystal. This reorganization is almost the same as that observed in NH(4)Cl and NH(4)I single crystals, although the latter two are characterized by different, simple cubic and face-centered cubic, structures. 相似文献
39.
Harsh Kumar Kanchan Bhardwaj Natlia Cruz-Martins Eugenie Nepovimova Patrik Oleksak Daljeet Singh Dhanjal Sonali Bhardwaj Reena Singh Chirag Chopra Rachna Verma Prem Parkash Chauhan Dinesh Kumar Kamil Ku
a 《Molecules (Basel, Switzerland)》2021,26(11)
The ingestion of contaminated water and food is known to cause food illness. Moreover, on assessing the patients suffering from foodborne disease has revealed the role of microbes in such diseases. Concerning which different methods have been developed for protecting food from microbes, the treatment of food with chemicals has been reported to exhibit an unwanted organoleptic effect while also affecting the nutritional value of food. Owing to these challenges, the demand for natural food preservatives has substantially increased. Therefore, the interest of researchers and food industries has shifted towards fruit polyphenols as potent inhibitors of foodborne bacteria. Recently, numerous fruit polyphenols have been acclaimed for their ability to avert toxin production and biofilm formation. Furthermore, various studies have recommended using fruit polyphenols solely or in combination with chemical disinfectants and food preservatives. Currently, different nanoparticles have been synthesized using fruit polyphenols to curb the growth of pathogenic microbes. Hence, this review intends to summarize the current knowledge about fruit polyphenols as antibacterial agents against foodborne pathogens. Additionally, the application of different fruit extracts in synthesizing functionalized nanoparticles has also been discussed. 相似文献
40.
Umakanta Tripathy R. Justin Rajesh Prem B. Bisht A. Subrahamanyam 《Journal of Chemical Sciences》2002,114(6):557-564
The excited state absorption cross-section of 5,5′-dichloro-11-diphenyl-amino-3,3′-diethyl-10, 12-ethylinethiatricarbocyanine
perchlorate (IR140) have been measured by using a single beam transmission technique. Z-scan experiments have been used to find out a few nonlinear
parameters. The excited state relaxation times have also been measured by using laser induced transient grating (LITG) technique. 相似文献