A facile synthesis of oxazines by indium-induced reduction-rearrangement of the nitro β-lactams

An indium-induced reduction-rearrangement reaction of nitro-substituted β-lactams has been used for facile synthesis of oxazines in aqueous ethanol.     

Microchemical characterization of paintings — A case study

Summary The fundamental importance of scientific research for the preservation and restoration of works of art is uncontestable. The methods described in this paper, such as light microscopy, microchemical tests, emission spectroscopy, chromatography, scanning electron analysis, electron microprobe analysis and infrared spectroscopy, are of special significance in this filed. Nevertheless a better understanding of the problems that arise out of new special questions of art history can be obtained only by the right interpretation of the data obtained by scientific methods.

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Mikrochemische Charakterisierung von Gemälden

Zusammenfassung Die grundlegende Bedeutung wissenschaftlicher Forschung für die Erhaltung und Restaurierung von Kunstwerken ist unbestritten. Die hier beschriebenen Methoden (Lichtmikroskopie, mikrochemische Reaktionen, Emissionsspektroskopie, Chromatographie, Rasterelektronen-Analyse und Infrarotspektroskopie) sind hierfür von zunehmender Bedeutung. Sie ermöglichen ein besseres Verständnis neuerer kunsthistorischer Probleme nur durch die richtige Interpretation der Ergebnisse wissenschaftlicher Methoden.

     

On the underestimated influence of synthetic conditions in solid ionic conductors

The development of high-performance inorganic solid electrolytes is central to achieving high-energy- density solid-state batteries. Whereas these solid-state materials are often prepared via classic solid-state syntheses, recent efforts in the community have shown that mechanochemical reactions, solution syntheses, microwave syntheses, and various post-synthetic heat treatment routines can drastically affect the structure and microstructure, and with it, the transport properties of the materials. On the one hand, these are important considerations for the upscaling of a materials processing route for industrial applications and industrial production. On the other hand, it shows that the influence of the different syntheses on the materials'' properties is neither well understood fundamentally nor broadly internalized well. Here we aim to review the recent efforts on understanding the influence of the synthetic procedure on the synthesis – (micro)structure – transport correlations in superionic conductors. Our aim is to provide the field of solid-state research a direction for future efforts to better understand current materials properties based on synthetic routes, rather than having an overly simplistic idea of any given composition having an intrinsic conductivity. We hope this review will shed light on the underestimated influence of synthesis on the transport properties of solid electrolytes toward the design of syntheses of future solid electrolytes and help guide industrial efforts of known materials.

Influence of synthesis and processing on the nature of ultimate product and the ionic transport properties of superionic conductors.     

Reversed phase chromatographic separation of zirconium,niobium and hafnium tracers with HDEHP

Effective separation of the congeneric pair of elements, zirconium and hafnium and also niobium which was in admixtures with zirconium as daughter in its isotopic form were achieved through reversed phase column and paper extraction chromatographic procedures using di-(2-ethylhexyl)phosphoric acid (HDEHP) as the liquid exchanger. In reversed phase column chromatographic separation, the tracers,⁹⁵Zr,⁹⁵Nb and^175,181Hf, were extracted by HDEHP impregnated on kieselguhr and were sequentially eluted with 6N H₂SO₄+xN oxalic acid+H₂O₂(where x=0.1, 0.5 and 2). Similarly, in reversed phase paper chromatographic study in which a coating of HDEHP on Whatman No. 1 chromatographic paper was used as stationary phase, the mobile phase, 18N H₂SO₄+0.1N oxalic acid + H₂O₂, helped in separating the elements with favorable separation factors. Under the optimal conditions, the separation and decontamination of the elements in both methods were found to be quantitative, as verified by -spectrometric studies.     

Mimicking transition metals in borrowing hydrogen from alcohols

Borrowing hydrogen from alcohols, storing it on a catalyst and subsequent transfer of the hydrogen from the catalyst to an in situ generated imine is the hallmark of a transition metal mediated catalytic N-alkylation of amines. However, such a borrowing hydrogen mechanism with a transition metal free catalytic system which stores hydrogen molecules in the catalyst backbone is yet to be established. Herein, we demonstrate that a phenalenyl ligand can imitate the role of transition metals in storing and transferring hydrogen molecules leading to borrowing hydrogen mediated alkylation of anilines by alcohols including a wide range of substrate scope. A close inspection of the mechanistic pathway by characterizing several intermediates through various spectroscopic techniques, deuterium labelling experiments, and DFT study concluded that the phenalenyl radical based backbone sequentially adds H⁺, H˙ and an electron through a dearomatization process which are subsequently used as reducing equivalents to the C–N double bond in a catalytic fashion.

An efficient method is developed for harvesting hydrogen, its storage and catalytic transfer by an odd alternant hydrocarbon. The strategy is reminiscent of transition metals in borrowing hydrogen mediated processes.     

Polyether azomethines. I. Synthesis and characterization

Six new polyether azomethines were synthesized by melt and solution polycondensation of six different diamines with 4,4′-[1,4-phenylene bis(oxy)] bisbenzaldehyde. The polymers synthesized by solution method are yellow to white in color and had inherent viscosities up to 0.59 dL/g in concentrated H₂SO₄. The polymers obtained by melt condensation show higher viscosity. Except polymer IV , others are insoluble in common organic solvents. The polymers were characterized by IR, x-ray, elemental analysis, and DSC study. The thermal stability of the polymers was evaluated by TGA and IGA study. Polymers I-III are highly thermally and thermooxidatively stable and exhibit no appreciable decomposition up to 420°C both in air and nitrogen atmosphere. It was shown that the curing of the polyazo-methines takes place by opening up of the ? CH?N? linkages at higher temperature. The electrical conductivities of the virgin and iodine doped polymers were as high as 10^?11?10^?16 and 10^?6?10^?8S cm^?1, respectively, at 30°C. Electronic spectra of the undoped polymers ( I-III ) indicated a large bathochromic shift of the ? – ?^* absorptions band (376 nm) due to ? C?N? bonds of the model compound. This can be attributed to extensive delocalization of the electrons along the polymer chain. © 1995 John Wiley & Sons, Inc.     

Effect of environmental factors and carbohydrate on gellan gum production

Submerged culture fermentation studies were carried out in batch mode for optimizing the environmental parameters and carbon source requirement by Pseudomonas elodea for the production of gellan gum. The maximum production of gellan gum was obtained with 16-h-old culture and 8% inoculum at 30°C and pH 7.0 after 52 h of incubation (6.0 g/L). Of the various carbon sources tested, 2% sucrose, glucose, and soluble starch yielded considerably high amounts of gellan. Studies on the concentration of various carbohydrates on gellan gum production indicated that the optimum concentration of glucose and starch was 3%, whereas for sucrose it was 4%. The addition of glucose in the medium above 3% had a detrimental effect on gellan yield. The investigation of intermediate two-step addition of glucose under identical conditions of fermentation showed an enhanced production of gellan (8.12 g/L) as compared with the control (6.0 g/L). To optimize the recovery of gellan from fermented broth, different solvents were tested for precipitation of gellan gum. Among the various solvents tested, tetrahydrofuran gave better recovery of gellan (82%) as compared with the conventional solvent isopropanol (49%).     

Microwave-induced organic reaction enhancement (more) chemistry: Techniques for rapid,safe and inexpensive synthesis

Synthetic organic reactions have been conducted under microwave irradiation in open vessels in unaltered domestic microwave ovens. Reaction times vary from a few seconds for sub-milligram reactions to about 15 minutes for reactions carried out on a scale of hundreds of grams. Promising results have been obtained for several condensations, as well as the Bischler-Napieralski reaction, the Wolff-Kishner reduction, free radical dehalogenation reactions, and other standard synthetic operations. Rapid catalytic transfer hydrogenation using ammonium formate as the source of hydrogen has been conducted at about 100-130 °C under microwave irradiation. Meaningful, safe and inexpensive synthetic experiments for undergraduate and pre-college students have been developed and tested. The MORE chemistry techniques make it possible to use simple apparatus and very short reaction times. Commercial microwave ovens are now essential equipment in our research and teaching laboratories [1-3]. These ovens are relatively inexpensive, easy to move from one laboratory and set up in another, and safe to operate. Glass, plastics, and ceramics are essentially transparent to microwaves whereas many organic compounds are dipolar in nature and absorb microwave energy readily. We have found that untraditional experimental arrangements are possible for conducting a wide variety of organic reactions in open vessels inside domestic microwave ovens. Depending on the quantity of reactants, most reactions (on a scale of milligrams to several grams) can be completed in minutes instead of hours. One important element of our “Microwave-induced Organic Reaction Enhancement” (MORE) chemistry is the proper choice of a microwave energy transfer agent as the reaction medium.     

Oxomolybdenum(VI) and (IV) complexes of pyrazole derived ONO donor ligands – synthesis,crystal structure studies and spectroelectrochemical correlation

Four cis-dioxomolybdenum complexes of general formula [MoO₂(Lⁿ)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L⁴)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh₃. The complexes are characterized by elemental analysis, electronic spectra, IR, ¹H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO₅ donor environment.     

Time-dependent quantum wave-packet description of the 1pi sigma* photochemistry of phenol

The photoinduced hydrogen elimination reaction in phenol via the conical intersections of the dissociative 1pi sigma* state with the 1pi pi* state and the electronic ground state has been investigated by time-dependent quantum wave-packet calculations. A model including three intersecting electronic potential-energy surfaces (S0, 1pi sigma*, and 1pi pi*) and two nuclear degrees of freedom (OH stretching and OH torsion) has been constructed on the basis of accurate ab initio multireference electronic-structure data. The electronic population transfer processes at the conical intersections, the branching ratio between the two dissociation channels, and their dependence on the initial vibrational levels have been investigated by photoexciting phenol from different vibrational levels of its ground electronic state. The nonadiabatic transitions between the excited states and the ground state occur on a time scale of a few tens of femtoseconds if the 1pi pi*-1pi sigma* conical intersection is directly accessible, which requires the excitation of at least one quantum of the OH stretching mode in the 1pi pi* state. It is shown that the node structure, which is imposed on the nuclear wave packet by the initial preparation as well as by the transition through the first conical intersection (1pi pi*-1pi sigma*), has a profound effect on the nonadiabatic dynamics at the second conical intersection (1pi sigma*-S0). These findings suggest that laser control of the photodissociation of phenol via IR mode-specific excitation of vibrational levels in the electronic ground state should be possible.