Where on Earth has our water come from?

The presence of water in the Earth has long been an enigma. However, computer modelling techniques have shown that the adsorption of water onto the fractal surfaces of interplanetary dust particles, which are present in the planetary accretion disk, is sufficiently strong to provide a viable origin of terrestrial water.     

Simulating Suppression Effects in Pulsed ENDOR, and the ‘Hole in the Middle’ of Mims and Davies ENDOR Spectra

All pulsed electron-nuclear double resonance (ENDOR) techniques, and in particular the Mims and Davies sequences, suffer from detectability biases (‘blindspots’) that are directly correlated to the size of the hyperfine interactions of coupled nuclei. Our efforts at ENDOR ‘crystallography’ and ‘mechanism determination’ with these techniques have led our group to refine our simulations of pulsed ENDOR spectra to take into account these biases, and we here describe the process and illustrate it with several examples. We first focus on an issue whose major significance is not widely appreciated, the ‘hole in the middle’ of pulsed ENDOR spectra caused by the n = 0 suppression hole in Mims ENDOR and by the analogous A → 0 suppression in Davies ENDOR for I = ½ and for ²H (I = 1). We then discuss the general treatment of suppression effects for I = 1, illustrating it with a treatment of Mims suppression for ¹⁴N.     

Photoluminescence, optical absorption and XRD studies on X-ray irradiated terbium doped KBr crystals

This paper reports the optical absorption, photoluminescence (PL), XRD, SEM studies made on KBr:Tb³⁺ crystals. The integrated light intensity is enhanced by about two orders of magnitude as compared to the undoped samples in spite of some OH^- present in the samples. PL of these crystals exhibits characteristic Tb³⁺ emissions due to transitions from the ⁵D₃ to ⁵D₄ levels to various levels of the ⁷F septet on F-bleaching X-ray irradiated crystals Z₃ centers are observed. The bands observed in the emission spectra of Tb³⁺ doped KBr are found to be shifted to higher wavelength. The stokes-shift of KBr:Tb³⁺ is determined and it is found to have a large value. The XRD studies have been made to determine the crystalline structure of KBr and KBr:Tb³⁺ and also the Miller indices. The SEM studies made reveal the presence of microcrystalline structure.     

Deprotection of oximes using urea nitrate under microwave irradiation

A new mild and efficient method for the cleavage of oximes to carbonyl compounds using readily available urea nitrate in acetonitrile-water (95:5), under microwave irradiation within 2 min, in good yields is reported     

Novel Sulfamic Acid–Promoted Synthesis of 3-Alkylidene Indolone Derivatives in the Presence of Aniline via One-Pot Multicomponent Reaction

A sulfamic acid–catalyzed synthesis of 3-alkylidene indolone derivatives by addition of dialkyl acetylenedicarboxylate to isatin derivatives in the presence of aniline is reported. The reaction sequence consists of an initial Michael addition of aniline to dialkyl acetylenedicarboxylate, followed by aldol-like reaction with isatin, and then elimination of aniline to afford the product.     

A Short and Convenient Synthesis of 5-Alkyl Substituted 8-Hydroxyquinolines

5-Chloro-8-methoxyquinoline undergoes rapid and reversible lithium-halogen exchange reaction with alkyllithiums to yield 5-alkyl substituted derivatives indirectly, whereas the reaction with phenyllithium is slower and 5-alkyl substituted compounds are formed by the direct addition of alkyl halides.     

Active Intermediates in Copper Nitrite Reductase Reactions Probed by a Cryotrapping-Electron Paramagnetic Resonance Approach

Redox active metalloenzymes catalyse a range of biochemical processes essential for life. However, due to their complex reaction mechanisms, and often, their poor optical signals, detailed mechanistic understandings of them are limited. Here, we develop a cryoreduction approach coupled to electron paramagnetic resonance measurements to study electron transfer between the copper centers in the copper nitrite reductase (CuNiR) family of enzymes. Unlike alternative methods used to study electron transfer reactions, the cryoreduction approach presented here allows observation of the redox state of both metal centers, a direct read-out of electron transfer, determines the presence of the substrate/product in the active site and shows the importance of protein motion in inter-copper electron transfer catalyzed by CuNiRs. Cryoreduction-EPR is broadly applicable for the study of electron transfer in other redox enzymes and paves the way to explore transient states in multiple redox-center containing proteins (homo and hetero metal ions).     

Effect of piperidones on hydrogen permeation and corrosion inhibition of mild steel in acidic solutions

The influence of 3-methyl-2,6-diphenyl piperidin-4-one (MDPO) and 2-phenyl decahydroquinoline-4-one (PDQO) synthesised in the laboratory on hydrogen permeation and corrosion inhibition of mild steel in 1N H₂SO₄ has been studied using weight loss and various electrochemical AC and DC corrosion-monitoring techniques. Both the compounds inhibit the corrosion of mild steel in H₂SO₄. Potentiodynamic polarisation studies clearly reveal that they behave predominantly as cathodic inhibitors. The extent of decrease in hydrogen permeation current through steel surfaces has been studied by the hydrogen electropermeation technique. Double layer capacitance (C _dl ) and charge transfer resistance (R _t ) values are derived from Nyquist plots obtained from AC impedance studies. The adsorption of these compounds on mild steel surfaces from H₂SO₄ obeys Temkin’s adsorption isotherm.