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81.
Adair Gallo Jr. Nayara H. Musskopf Xinlei Liu Ziqiang Yang Jeferson Petry Peng Zhang Sigurdur Thoroddsen Hong Im Himanshu Mishra 《Chemical science》2022,13(9):2574
Recent reports on the formation of hydrogen peroxide (H2O2) in water microdroplets produced via pneumatic spraying or capillary condensation have garnered significant attention. How covalent bonds in water could break under such mild conditions challenges our textbook understanding of physical chemistry and water. While there is no definitive answer, it has been speculated that ultrahigh electric fields at the air–water interface are responsible for this chemical transformation. Here, we report on our comprehensive experimental investigation of H2O2 formation in (i) water microdroplets sprayed over a range of liquid flow-rates, (shearing) air flow rates, and air composition, and (ii) water microdroplets condensed on hydrophobic substrates formed via hot water or humidifier under controlled air composition. Specifically, we assessed the contributions of the evaporative concentration and shock waves in sprays and the effects of trace O3(g) on the H2O2 formation. Glovebox experiments revealed that the H2O2 formation in water microdroplets was most sensitive to the air–borne ozone (O3) concentration. In the absence of O3(g), we could not detect H2O2(aq) in sprays or condensates (detection limit ≥250 nM). In contrast, microdroplets exposed to atmospherically relevant O3(g) concentration (10–100 ppb) formed 2–30 µM H2O2(aq), increasing with the gas–liquid surface area, mixing, and contact duration. Thus, the water surface area facilitates the O3(g) mass transfer, which is followed by the chemical transformation of O3(aq) into H2O2(aq). These findings should also help us understand the implications of this chemistry in natural and applied contexts.A. Gallo Jr, H. Mishra et al., pinpoint the origins of the spontaneous H2O2 formation in water microdroplets formed via spraying or condensation, i.e., without the addition of electrical energy, catalyst, or co-solvent. 相似文献
82.
Prasad Mishra G Venkata Ramana G Venkateswara Rao B 《Chemical communications (Cambridge, England)》2008,(29):3423-3425
A new, efficient and highly diastereoselective approach for the synthesis of 1,2,3,5-tetraacetylcarba-alpha-D-lyxofuranose from D-ribose is reported via one-pot conversion of to using Tebbe reagent which involves a cascade reaction sequence of methylenation, cleavage of isopropyl group, carbocyclization and again methylenation. 相似文献
83.
The condensation of 3-amino-1H-1,2,4-triazole with benzaldehyde and terephthalaldehyde provides the bidentate and tetradentate Schiff bases 1,2,4-triazolo-3-imino-benzene L1H and 1,4-bis(1,2,4-triazolo-3-imino)benzene L2H2, respectively. The well characterized Schiff bases were allowed to react with cis-Ru(bpy)2Cl2 · 2H2O. Isomers of the mononuclear complexes Ru(bpy)2L1]PF6 · NH4PF6 (1a, N4) and [Ru(bpy)2L1]PF6 · 0.5NH4PF6 (1b, N2), and the dinuclear Ru(II) complexes [Ru(bpy)2L2Ru(bpy)2](PF6)2 · NH4PF6 (2a, N4N4), [Ru(bpy)2L2Ru(bpy)2](PF6)2 · NH4PF6 · 2H2O (2b, N2N2) and [Ru(bpy)2L2Ru(bpy)2](PF6)3 · NH4PF6 (2c, Ru(II)-Ru(III)) were separated by column chromatography and characterized by their elemental analysis, FAB mass and spectral (IR, NMR, UV–Vis) data. The data obtained suggest that the ligands are bound to the metal centre via the N4 and N2 atoms of the triazole moiety along with the N (imine) atom. The complexes display metal-to-ligand charge-transfer (MLCT) transitions in the visible region from the dπ(RuII) → π∗L transition. Highly intense ligand-based π→π∗ transitions are observed in the UV region. A dual emission occurs from the N2 and N2N2 isomers. 相似文献
84.
Reactions of peroxynitrite with guanine were investigated using density functional theory (B3LYP) employing 6-31G** and AUG-cc-pVDZ basis sets. Single point energy calculations were performed at the MP2/AUG-cc-pVDZ level. Genuineness of the calculated transition states (TS) was tested by visually examining the vibrational modes corresponding to the imaginary vibrational frequencies and applying the criterion that the TS properly connected the reactant and product complexes (PC). Genuineness of all the calculated TS was further ensured by intrinsic reaction coordinate (IRC) calculations. Effects of aqueous media were investigated by solvating all the species involved in the reactions using the polarizable continuum model (PCM). The calculations reveal that the most stable nitro-product complex involving the anion of 8-nitroguanine and a water molecule i.e. 8NO(2)G(-) + H(2)O can be formed according to one reaction mechanism while there are two possible reaction mechanisms for the formation of the oxo-product complex involving 8-oxoguanine and anion of the NO(2) group i.e. 8OG + NO(2)(-). The calculated relative stabilities of the PC, barrier energies of the reactions and the corresponding enthalpy changes suggest that formation of the complex 8OG + NO(2)(-) would be somewhat preferred over that of the complex 8NO(2)G(-) + H(2)O. The possible biological implications of this result are discussed. 相似文献
85.
Mishra A Tasiopoulos AJ Wernsdorfer W Abboud KA Christou G 《Inorganic chemistry》2007,46(8):3105-3115
The syntheses, structures, and magnetic properties are reported of the mixed-metal complexes [Ce4Mn10O10(OMe)6(O2CPh)16(NO3)2(MeOH)2(H2O)2] (1) and [Th6Mn10O22(OH)2(O2CPh)16-(NO3)2(H2O)8] (2), which were both prepared by the reaction of (NBun4)[Mn4O2(O2CPh)9(H2O)] (3) with a source of the heterometal in MeCN/MeOH. Complexes 1 and 2 crystallize in the monoclinic space group C2/c and the triclinic space group P, respectively. Complex 1 consists of 10 MnIII, 2 CeIII, and 2 CeIV atoms and possesses a very unusual tubular [Ce4Mn10O10(OMe)6]18+ core. Complex 2 consists of 10 MnIV and 6 ThIV atoms and possesses a [Th6Mn10O22(OH)2]18+ core with the metal atoms arranged in layers with a 2:3:6:3:2 pattern. Peripheral ligation around the cores is provided by 16 bridging benzoates, 2 chelating nitrates, and either (i) 2 each of terminal H2O and MeOH groups in 1 or (ii) 8 terminal H2O groups in 2. Complex 1 is the largest mixed-metal Ce/Mn cluster and the first 3d/4f cluster with mixed-valency in its lanthanide component, while complex 2 is the first Th/Mn cluster and the largest mixed transition metal/actinide cluster to date. Solid-state dc and ac magnetic susceptibility measurements on 1 and 2 establish that they possess S = 4 and 3 ground states, respectively. Ac susceptibility studies on 1 revealed nonzero frequency-dependent out-of-phase (chiM' ') signals at temperatures below 3 K; complex 2 displays no chiM' ' signals. However, single-crystal magnetization vs dc field scans at variable temperatures and variable sweep-rates down to 0.04 K on 1 revealed no noticeable hysteresis loops, except very minor ones at 0.04 K assignable to weak intermolecular interactions propagated by hydrogen bonds involving CeIII-bound ligands. Complex 1 is thus concluded not to be a single-molecule magnet (SMM), and the combined results thus represent a caveat against taking such ac signals as sufficient proof of a SMM. 相似文献
86.
Tiwari AD Mishra AK Mishra SB Mamba BB Maji B Bhattacharya S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):1050-1056
The thiocarbohydrazone Schiff-base ligand with a nitrogen and sulphur donor was synthesized through condensation of pyridine-2-carbaldehyde and thiocarbohydrazide. Schiff-base ligands have the ability to conjugate with metal salts. A series of metal complexes with a general formula [MCl2(H2L)]·nH2O (MNi, Co, Cu and Zn) were synthesized by forming complexes of the N1,N5-bis[pyridine-2-methylene]-thiocarbohydrazone (H2L) Schiff-base ligand. These metal complexes and ligand were characterized by using ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FT-IR), 1H and 13C NMR spectroscopy and mass spectroscopy, physicochemical characterization, CHNS and conductivity. The biological activity of the synthesized ligand was investigated by using Escherichia coli DNA as target. The DNA interaction of the synthesized ligand and complexes on E. coli plasmid DNA was investigated in the aqueous medium by UV-Vis spectroscopy and the binding constant (Kb) was calculated. The DNA binding studies showed that the metal complexes had an improved interaction due to trans-geometrical isomers of the complexes than ligand isomers in cis-positions. 相似文献
87.
A. K. Chaturvedi D. Chaturvedi N. Mishra V. Mishra 《Journal of the Iranian Chemical Society》2011,8(2):396-400
A novel Mitsunobu-based protocol has been developed for the synthesis of carbazates and dithiocarbazates through the variety of corresponding primary, secondary and tertiary alcohols and various kinds of substituted hydrazines using Mitsunobu??s reagent and CO2/CS2 system, in good to excellent yields. 相似文献
88.
M. S. Mehmood Hafeez-Ullah M. S. Jahan S. Mishra B. M. Walters M. Ikram 《Polymer Science Series A》2012,54(5):343-348
Powder samples of UHMWPE (GUR 1020) containing 0.1% by wt. vitamin E (??-tocopherol, ??-T) were irradiated at room temperature in air for doses of 30-kGy, 65-kGy or 100-kGy (60Co). After irradiation, they were stored at ?78.5°C (dry ice temperature) for one year and then opened to air at room temperature. Following the decay of the primary alkyl and allyl radicals (at room temperature in air), growth of the carbon-centered polyenyl R1 (?·CH?CH=CH?, m ?? 3), and the oxygen-centered dior tri-enyl R2 (?·OCH?CH=CH? m , m ?? 3) residual radicals were measured for eight weeks. An X-band electron spin resonance (ESR) spectrometer was used for radical measurements. The initial relative radical concentrations (R2/R1) were found to be 10.13, 4.6 and 3.7 for the 65-kGy, 30-kGy and 100-kGy samples, respectively. R1 and R2 were both found to grow significantly in the 65-kGy samples while they grew only slightly in the 30-kGy and 100-kGy samples. In 65-kGy sample, R1 grew faster than R2 and the relative concentration R2/R1 was reduced from 10.13 to 2.9 for the 65-kGy sample while that for the 30-kGy and 100-kGy samples reduced only slightly, from 4.6 to 3.5 and 3.7 to 3.2, respectively. The behavior of the residual radicals can be explained by Raman spectroscopic data which suggest that the 65-kGy samples had a higher percentage of amorphous regions when compared to the 30-kGy or 100-kGy (21.7% compared to 15.7% or 17.9%) and also suggest a lower percentage of inter-phase regions (16.4% compared to 25.6% or 17.5%) and a lower level of structural disorder (0.26% compared to 0.44% or 0.27%). 相似文献
89.
90.
Mishra R. Ali M. Bharadwaj S. R. Das D. 《Journal of Thermal Analysis and Calorimetry》2001,66(3):779-784
Cesium zirconate and cesium thorate were prepared by sol-gel method following citrate-nitrate route. The compounds were characterized
by X-ray diffraction, chemical analysis and simultaneous TG-DTA. The methods of preparation of Cs2ZrO3 and Cs2ThO3 reported in literature involve difficult steps and require stringent experimental conditions for obtaining the compounds.
In this work we report an easier method for the preparation of these compounds at relatively low temperature.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献