A new half-condensed Schiff base compound: highly selective and sensitive pH-responsive fluorescent sensor

A new probe, 3-[(3-benzyloxypyridin-2-ylimino)methyl]-2-hydroxy-5-methylbenzaldehyde (1-H) behaves as a highly selective fluorescent pH sensor in a Britton-Robinson buffer at 25 °C. The pH titrations show a 250-fold increase in fluorescence intensity within the pH range of 4.2 to 8.3 with a pK(a) value of 6.63 which is valuable for studying many of the biological organelles.     

Synthesis of Heterocycles by isothiourea organocatalysis

Isothiourea was first employed as catalyst by Birman in 2006 for the enantioselective acyl transfer reaction. The catalyst was then well explored in the course of kinetic resolution and desymmetrization studies. A few years later, Romo and Smith applied isothiourea catalysis in enantioselective cascade reactions to prepare carbocycles and heterocycles acessing new reactivities of isothiourea. Several research groups were then attracted toward this new field of organocatalysis, and applied isothioureas as nucleophilic catalysts in executing cascade methodologies to synthesize various intresteting molecular scaffolds including heterocycles. The present review documents a summary on the construction of heterocyclic molecules by isothiourea organocatalysis. Heterocycles are of prime interest to organic chemists due to their omnipresence in natural products and bioactive molecules. The Lewis basic nucleophilic catalyst isothioureas play a pivotal role in the cascades to generate either α,β-unsaturated acyl isothiouronium ion or isothiouronium enolate as the prime reaction intermediate. We have covered the reactions involving two intermediates of opposite reactivities affording various heterocycles.     

Fast Hydrocarbon Oxidation by a High-Valent Nickel–Fluoride Complex

In the search for highly reactive oxidants we have identified high-valent metal–fluorides as a potential potent oxidant. The high-valent Ni–F complex [Ni^III(F)(L)] ( 2 , L=N,N′-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamidate) was prepared from [Ni^II(F)(L)]⁻ ( 1 ) by oxidation with selectfluor. Complexes 1 and 2 were characterized by using ¹H/¹⁹F NMR, UV-vis, and EPR spectroscopies, mass spectrometry, and X-ray crystallography. Complex 2 was found to be a highly reactive oxidant in the oxidation of hydrocarbons. Kinetic data and products analysis demonstrate a hydrogen atom transfer mechanism of oxidation. The rate constant determined for the oxidation of 9,10-dihydroanthracene (k₂=29 m ⁻¹ s⁻¹) compared favorably with the most reactive high-valent metallo-oxidants. Complex 2 displayed reaction rates 2000–4500-fold enhanced with respect to [Ni^III(Cl)(L)] and also displayed high kinetic isotope effect values. Oxidative hydrocarbon and phosphine fluorination was achieved. Our results provide an interesting direction in designing catalysts for hydrocarbon oxidation and fluorination     

Photocatalytic degradation of carcinogenic Congo red dye in aqueous solution,antioxidant activity and bactericidal effect of NiO nanoparticles

Journal of the Iranian Chemical Society - Face-centered cubic structure of nickel oxide (NiO) nanoparticles with 30 nm average size was synthesized by co-precipitation method with some...     

Remarkable Energy Barrier for Magnetization Reversal in 3D and 2D Dysprosium-Chloranilate-Based Coordination Polymers

Herein, two coordination polymers (CPs) [{Dy(Cl₂An)_1.5(CH₃OH)} ⋅ 4.5 H₂O]_n ( 1 ) and [Dy(Cl₂An)_1.5(DMF)₂]_n ( 2 ), in which Cl₂An is chloranilate (2,5-dihydroxy-1,4-benzoquinone dianion), exhibiting field-induced single-molecule magnet behavior with moderate barrier of magnetization reversal are reported. Detailed structural and topological analysis disclosed that 1 has a 3D network, whereas 2 has a 2D layered-type structure. In both CPs, magnetic measurements showed weak antiferromagnetic exchange interaction between the dysprosium centers and field-induced slow magnetic relaxation with barriers of 175(9)K and 145(7)K for 1 and 2 , respectively. Notably, the energy barriers of magnetization reversal of 1 and 2 are remarkable for metal–chloranilate-based 3D ( 1 ) and 2D ( 2 ) CPs. The temperature and field dependence of relaxation time indicate the presence of multiple relaxation pathways, such as direct, quantum tunneling of magnetization, Raman, and Orbach processes, in both CPs. Ab initio theoretical calculations reinforced the experimentally observed higher energy barrier in 1 as compared with 2 due to the presence of large transverse anisotropy in the ground state in the latter. The average transition magnetic moment between the computed low-lying spin–orbit states also rationalized the relaxation as Orbach and Raman processes through the first excited state. BS-DFT calculations were carried out for both CPs to provide more insight into the exchange interaction.     

A “Thermodynamically Stable” 2D Nickel Metal–Organic Framework over a Wide pH Range with Scalable Preparation for Efficient C2s over C1 Hydrocarbon Separations

The design and construction of “thermodynamically stable” metal–organic frameworks (MOFs) that can survive in liquid water, boiling water, and acidic/basic solutions over a wide pH range is highly desirable for many practical applications, especially adsorption-based gas separations with obvious scalable preparations. Herein, a new thermodynamically stable Ni MOF, {[Ni(L)(1,4-NDC)(H₂O)₂]}_n (IITKGP-20; L=4,4′-azobispyridine; 1,4-NDC=1,4-naphthalene dicarboxylic acid; IITKGP stands for the Indian Institute of Technology Kharagpur), has been designed that displays moderate porosity with a BET surface area of 218 m² g⁻¹ and micropores along the [10−1] direction. As an alternative to a cost-intensive, cryogenic, high-pressure distillation process for the separation of hydrocarbons, MOFs have recently shown promise for such separations. Thus, towards an application standpoint, this MOF exhibits a higher uptake of C₂ hydrocarbons over that of C₁ hydrocarbon under ambient conditions, with one of the highest selectivities based on the ideal adsorbed solution theory (IAST) method. A combination of two strategies (the presence of stronger metal–N coordination of the spacer and the hydrophobicity of the aromatic moiety of the organic ligand) possibly makes the framework highly robust, even stable in boiling water and over a wide range of pH 2–10, and represents the first example of a thermodynamically stable MOF displaying a 2D structural network. Moreover, this material is easily scalable by heating the reaction mixture at reflux overnight. Because such separations are performed in the presence of water vapor and acidic gases, there is a great need to explore thermodynamically stable MOFs that retain not only structural integrity, but also the porosity of the frameworks.     

Reduced-order modelling of thermoacoustic instabilities in a two-heater Rijke tube

The topic of thermoacoustic instabilities in combustors is well-investigated, as it is important in the field of combustion, primarily in gas-turbine engines. In recent years, much attention has been focused on monitoring, diagnosis, prognosis, and control of high-amplitude pressure oscillations in confined combustion chambers. The Rijke tube is one of the most simple, yet very commonly used, laboratory apparatuses for emulation of thermoacoustic instabilities, which is also capable of capturing the physics of the thermally driven acoustics. A Rijke tube apparatus can be constructed with an electrical heater acting as the heat source, thus making it more flexible to operate and safer to handle than a fuel-burning Rijke tube or a fuel-fired combustor. Augmentation of the heat source of the Rijke tube with a secondary heater at a downstream location facilitates better control of thermoacoustic instabilities. Along this line, much work has been reported on the investigation of thermoacoustics by using computational fluid dynamics (CFD) modelling as well as reduced-order modelling for both single-heater and two-heater Rijke tube systems. However, since reduced-order models are often designed and built upon certain empirical relations, they may not account for the dynamic behaviour of the heater itself, which is a critical factor in the analysis and synthesis of real-time robust control systems. This issue is addressed in the current paper, where modifications have been made to existing models by incorporating heater dynamics. The model results are systematically validated with experimental data, generated from an in-house (electrically heated) Rijke tube apparatus.     

Signature of chaos and multistability in a Thomas-Fermi plasma

The European Physical Journal Special Topics - We propose a dynamical system governing from the nonlinear extension of the electrostatic ion-acoustic waves (IAWs) under the influence of external...     

Kinetics and thermodynamic analysis of maize cob pyrolysis for its bioenergy potential using thermogravimetric analyzer

Journal of Thermal Analysis and Calorimetry - The purpose of the study was to inspect the thermal degradation behavior of maize cob to find out its pyrolytic behavior for bioenergy generation....     

Dehalogenation of Halogenated Nucleobases and Nucleosides by Organoselenium Compounds

Halogenated nucleosides, such as 5-iodo-2′-deoxyuridine and 5-iodo-2′-deoxycytidine, are incorporated into the DNA of replicating cells to facilitate DNA single-strand breaks and intra- or interstrand crosslinks upon UV irradiation. In this work, it is shown that the naphthyl-based organoselenium compounds can mediate the dehalogenation of halogenated pyrimidine-based nucleosides, such as 5-X-2′-deoxyuridine and 5-X-2′-deoxycytidine (X=Br or I). The rate of deiodination was found to be significantly higher than that of the debromination for both nucleosides. Furthermore, the deiodination of iodo-cytidines was found to be faster than that of iodo-uridines. The initial rates of the deiodinations of 5-iodocytosine and 5-iodouracil indicated that the nature of the sugar moiety influences the kinetics of the deiodination. For both the nucleobases and nucleosides, the deiodination and debromination reactions follow a halogen-bond-mediated and addition/elimination pathway, respectively.