Alkoxybromination of Olefins Using Ammonium Bromide and Oxone

A mild, efficient, and highly regio- and stereoselective method for the methoxy and ethoxy bromination of olefins has been developed using NH₄Br as a bromine source and Oxone as an oxidant. Various kinds of olefins (aromatic, linear, and cyclic olefins) afforded the corresponding alkoxy brominated products in moderate to excellent yields.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resources: Full experimental and spectral details.]     

An enantioselective synthesis of a MEM-protected aetheramide A derivative

Aetheramides A and B are very potent anti-HIV agents. An enantioselective synthesis of a MEM-protected aetheramide A derivative is described. The synthesis was accomplished in a convergent and stereoselective manner. The key reactions involved asymmetric dihydroxylation, asymmetric allylation, asymmetric syn-aldol reactions, and asymmetric hydrogenation.     

Hydrogen bonding interaction and topological insights of the electron localization/delocalization of l- arginine acetate

The vibrational spectral studies of the semi-organic material l- arginine acetate (LAA) are carried out with the help of density functional calculations to derive the equilibrium geometry as well as the vibrational wavenumbers and intensities of the spectral bands. The vibrational spectrum assignments are performed using normal coordinate analysis (NCA) in accordance with the scaled quantum mechanical force field approach (SQMFF). Vibrational spectra confirm the COO- modes split due to intra- and intermolecular association based on C–O….H, N–H….O, and O–H?O hydrogen bonding in the molecule, which lowers carboxylate wavenumbers. The natural bond orbital (NBO) analysis and DFT computations also confirm the occurrence of strong intra and intermolecular N–H?O and O–H?O ionic hydrogen bonding between charged species, providing the non-centrosymmetric structure in the LAA crystal.     

Quantum information cannot be completely hidden in correlations: implications for the black-hole information paradox

Can quantum-information theory shed light on black-hole evaporation? By entangling the in-fallen matter with an external system we show that the black-hole information paradox becomes more severe, even for cosmologically sized black holes. We rule out the possibility that the information about the in-fallen matter might hide in correlations between the Hawking radiation and the internal states of the black hole. As a consequence, either unitarity or Hawking's semiclassical predictions must break down. Any resolution of the black-hole information crisis must elucidate one of these possibilities.     

Thermally stimulated discharge current (TSDC) characteristics in β-phase PVDF–BaTiO3 nanocomposites

β-phase polyvinylidene fluoride (PVDF)–BaTiO₃ nanocomposite samples have been prepared by solution mixing method. XRD data represent that the crystallinity of PVDF decreases with increase in loading level of BaTiO₃ nanoparticles. DSC curve represents that the melting point of PVDF is lightly affected by loading concentration of BaTiO₃. The morphology and microstructure of PVDF and PVDF embedded by BaTiO₃ nanofillers were investigated by using inverted contrast microscopy (ICM) and scanning electron microscopy (SEM). FTIR interferrometry is proven that PVDF and BaTiO₃ are not chemically interacting; therefore, interaction of BaTiO₃ is van der Waals type of interaction. The thermally stimulated discharge current (TSDC) of PVDF and PVDF–BaTiO₃ nanocomposites sample was characterized by single peak. The observed TSDC peak is discussed on the basis of dipolar and interfacial polarization.     

Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency

Three new electron‐rich metal–organic frameworks ( MOF‐1 – MOF‐3 ) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the π‐electron density of the luminescent MOFs. Single‐crystal X‐ray structures have revealed that these MOFs form three‐dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron‐rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF‐1 and MOF‐2 exhibit superior sensitivity towards 4‐nitrotoluene (4‐NT) and 2,4‐dinitrotoluene (DNT) compared to 2,4,6‐trinitrotoluene (TNT) and 1,3,5‐trinitrobenzene (TNB). MOF‐3 , on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady‐state and time‐resolved fluorescence quenching associated with these interactions. Determination of static Stern–Volmer constants (K_S) as well as collisional constants (K_C) has revealed that MOF‐1 and MOF‐2 have higher K_S values with 4‐NT than with TNT, whereas for MOF‐3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.     

Comparative computational appraisal of supercritical CO2-based natural circulation loop: effect of heat-exchanger and isothermal wall

Journal of Thermal Analysis and Calorimetry - Natural circulation loop (NCL) is a geometrically simple heat transfer device in which fluid flow occurs due to density gradient of loop fluid, induced...     

Recent Advances in the Chemistry and Therapeutic Evaluation of Naturally Occurring and Synthetic Withanolides

Natural products are a major source of biologically active compounds that make promising lead molecules for developing efficacious drug-like molecules. Natural withanolides are found in many flora and fauna, including plants, algae, and corals, that traditionally have shown multiple health benefits and are known for their anti-cancer, anti-inflammatory, anti-bacterial, anti-leishmaniasis, and many other medicinal properties. Structures of these withanolides possess a few reactive sites that can be exploited to design and synthesize more potent and safe analogs. In this review, we discuss the literature evidence related to the medicinal implications, particularly anticancer properties of natural withanolides and their synthetic analogs, and provide perspectives on the translational potential of these promising compounds.     

The effect of ph and gas composition on the bubble fractionation of proteins

Studies were conducted to establish the effect of the variation of environmental factors on the separation occurring in protein systems, resulting from bubble fractionation in a bioreactor. The measure of separation was selected to be the separation ratio. This is defined to be the ratio of either the top or the middle position concentration in the vessel to the bottom concentration of the vessel. Invertase and α-amylase were the two “model” enzymes considered. It was observed that, under certain conditions, i.e., a combination of the nature of the sparging gas and the medium pH, varying degrees of protein separation were achieved. The pH of the system dramatically influenced the separation. It was found that the best separation occurred at a certain pH, assumed to be at or close to thepI of the protein in question. Furthermore, it was observed that systems sparged with CO₂ exhibited greater separation than systems sparged with air. In fact, in the case of invertase, almost threefold separation was observed at the top port when the solution was sparged with CO₂.