Effect of cloud on atmospheric ozone formation over Kolkata (22°34′N, 88°24′E), India

The paper presents the nature of variations of clouds and total ozone over Kolkata (22°34′N, 88°24′E), India. The low-level cloud over Kolkata has been noticed to occur for many days and nights, particularly in the months from June to September. The low level cloud occurrences were minimum in winter months. The effect of cloud occurrence on ozone concentration has been critically analyzed and explained. It has been observed that the concentration of ozone increased with the increase of cloud occurrence. The related possible chemical explanation for ozone production processes has been offered.     

A copper(II) complex of benzimidazole-based ligand: synthesis,structure, redox aspects and fluorescence properties

Employing 1-(2-methoxybenzyl)-2-(2-methoxyphenyl)-1H-benzimidazole (bpb) as a monodentate ligand, a new greenish-blue copper(II) complex, [Cu(bpb)₂(NO₃)₂] (1a), has been synthesized. 1a has been characterized analytically and spectroscopically. The X-ray crystal structure of 1a reveals that it adopts a cis disposition with respect to the ligands. The solid state structure of 1a is stabilized by intramolecular offset face-to-face π–π stacking. Non-covalent supramolecular edge-to-face C–H?π interactions with neighboring molecules give 1-D supramolecular chains that further lead to the formation of an assembled 3-D supramolecular metal-organic framework via hydrogen bonding interactions. 1a shows blue fluorescence most likely due to intramolecular offset face-to-face π–π stacking. At room temperature, 1a is one-electron paramagnetic. It shows a rhombic EPR spectrum with g₁ = 2.12, g₂ = 2.42, and g₃ = 2.52 in the solid state at liquid nitrogen temperature. In cyclic voltammetry, 1a displays a one-electron oxidative Cu(II)/Cu(III) couple. Our DFT calculations, corroborate the observed experimental results of 1a.     

Boundaries of Anion/Naphthalenediimide Interactions: From Anion-π Interactions to Anion-Induced Charge-Transfer and Electron-Transfer Phenomena

The recent emergence of anion-π interactions has added a new dimension to supramolecular chemistry of anions. Yet, after a decade since its inception, actual mechanisms of anion-π interactions remain highly debated. To elicit a complete and accurate understanding of how different anions interact with π-electron-deficient 1,4,5,8-naphthalenediimides (NDIs) under different conditions, we have extensively studied these interactions using powerful experimental techniques. Herein, we demonstrate that, depending on the electron-donating abilities (Lewis basicity) of anions and electron-accepting abilities (π-acidity) of NDIs, modes of anion-NDI interactions vary from extremely weak non-chromogenic anion-π interactions to chromogenic anion-induced charge-transfer (CT) and electron-transfer (ET) phenomena. In aprotic solvents, electron-donating abilities of anions generally follow their Lewis basicity order, whereas π-acidity of NDIs can be fine-tuned by installing different electron-rich and electron-deficient substituents. While strongly Lewis basic anions (OH(-) and F(-)) undergo thermal ET with most NDIs, generating NDI(?-) radical anions and NDI(2-) dianions in aprotic solvents, weaker Lewis bases (AcO(-), H(2)PO(4)(-), Cl(-), etc.) often require the photoexcitation of moderately π-acidic NDIs to generate the corresponding NDI(?-) radical anions via photoinduced ET (PET). Poorly Lewis basic I(-) does not participate in thermal ET or PET with most NDIs (except with strongly π-acidic core-substituted dicyano-NDI) but forms anion/NDI CT or anion-π complexes. We have looked for experimental evidence that could indicate alternative mechanisms, such as a Meisenheimer complex or CH···anion hydrogen-bond formation, but none was found to support these possibilities.     

Hydrophobic Shielding of Outer Surface: Enhancing the Chemical Stability of Metal–Organic Polyhedra

Metal–organic polyhedra (MOP) are a promising class of crystalline porous materials with multifarious potential applications. Although MOPs and metal–organic frameworks (MOFs) have similar potential in terms of their intrinsic porosities and physicochemical properties, the exploitation of carboxylate MOPs is still rudimentary because of the lack of systematic development addressing their chemical stability. Herein we describe the fabrication of chemically robust carboxylate MOPs via outer‐surface functionalization as an a priori methodology, to stabilize those MOPs system where metal–ligand bond is not so strong. Fine‐tuning of hydrophobic shielding is key to attaining chemical inertness with retention of the framework integrity over a wide range of pH values, in strong acidic conditions, and in oxidizing and reducing media. These results are further corroborated by molecular modelling studies. Owing to the unprecedented transition from instability to a chemically ultra‐stable regime using a rapid ambient‐temperature gram‐scale synthesis (within seconds), a prototype strategy towards chemically stable MOPs is reported.     

Microwave assisted highly efficient one-pot multi-component synthesis of novel 2-(tetrasubstituted-1H-pyrrol-3-yl)-4H-chroman-4-ones catalyzed by heterogeneous reusable silica gel supported polyphosphoric acid (PPA/SiO2)

A solvent-free, eco-friendly and facile approach for the synthesis of highly functionalized tetrasubstituted pyrroles has been reported through one-pot four-component reaction of aldehyde, amine, nitroalkane and 1,3-diketone using silica gel supported polyphosphoric acid (PPA–SiO₂) under microwave condition. The reaction occured through the in situ formation of β-keto enamine and nitrostyrene analog following Michael addition and finally intramolecular annulation affording the products in good yields. The key features of the present method include clean reaction, mild conditions, low catalyst loading, straightforward, high to excellent yields, short reaction time, avoiding use of harmful metal catalyst and organic solvent, environmentally friendly compared to the existing methods, recovery and reusability of catalyst and easy workup procedure.     

Palladium(0) nanoparticles-catalyzed ligand-free direct arylation of benzothiazole via C-H bond functionalization

Palladium nanoparticles, generated in situ efficiently catalyzes direct 2-C-H arylation of benzothiazole without requirement of any ligand. A wide range of substituted aryl and heteroaryl iodides participate in this reaction producing a series of 2-aryl/heteroaryl-benzothiazoles in high yields.     

Titanocene (III) chloride mediated radical induced synthesis of (−)-methylenolactocin and (−)-protolichesterinic acid

Enantioselective synthesis of two anti-tumor antibiotics, (−)-methylenolactocin and (−)-protolichesterinic acid, has been achieved through titanocene(III) chloride mediated radical cyclization reaction starting from commercially available d-mannitol. Titanocene(III) chloride (Cp₂TiCl) was prepared in situ from commercially available titanocene dichloride (Cp₂TiCl₂) and zinc dust in THF.     

Modeling and experimental studies on combustion characteristics of porous coal char: Volume reaction model

A generalized single‐particle model for the prediction of combustion dynamics of a porous coal char in a fluidized bed is analyzed in the present work using a volume reaction model (VRM). A fully transient nonisothermal model involving both heterogeneous and homogeneous chemical reactions, multicomponent mass transfer, heat transfer with intraparticle resistances, as well as char structure evolution is developed. The model takes into account convection and diffusion inside the particle pores, as well as in the boundary layer. By addressing the Stefan flow originated due to nonequimolar mass transfer and chemical reactions, this work enables a more realistic analysis of the combustion process. The model, characterized by a set of partial differential equations coupled with nonlinear boundary conditions, is solved numerically using the implicit finite volume method (FVM) with a FORTRAN code developed in‐house. The use of a FVM for solving such an elaborate char combustion model, based on the VRM, was not reported earlier. Experiments consisting of fluidized‐bed combustion of a single char particle were carried out to determine the internal surface area of a partially burned char particle and to enable model validation. Predicted results are found to compare well with the reported experimental results for porous coal char combustion. The effects of various parameters (i.e., bulk temperature and initial particle radius) are examined on the dynamics of combustion of coal char. The phenomena of ignition and extinction are also investigated. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 299–315, 2010     

Thermohydraulics of turbulent flow through rectangular and square ducts with axial corrugation roughness and twisted-tapes with and without oblique teeth

The heat transfer and the pressure drop characteristics of turbulent flow of air (10,000 < Re < 100,000) through rectangular and square ducts with combined internal axial corrugations on all the surfaces of the ducts and with twisted-tape inserts with and without oblique teeth have been studied experimentally. The axial corrugations in combination with twisted-tapes of all types with oblique teeth have been found to perform better than those without oblique teeth in combination with axial corrugations. The heat transfer and the pressure drop measurements have been taken in separate test sections. Heat transfer tests were carried out in electrically heated stainless steel ducts incorporating uniform wall heat flux boundary conditions. Pressure drop tests were carried out in acrylic ducts. The flow friction and thermal characteristics are governed by duct aspect ratio, corrugation angle, corrugation pitch, twist ratio, space ratio, length, tooth horizontal length and tooth angle of the twisted-tape, Reynolds number and Prandtl number. Correlations developed for friction factor and Nusselt number have predicted the experimental data satisfactorily. The performance of the geometry under investigation has been evaluated. It has been found that on the basis of constant pumping power, up to 55% heat duty increase occurs for the combined axial corrugation and regularly spaced twisted-tape elements inserts with oblique teeth case compared to without oblique teeth twisted-tape inserts cases in the measured experimental parameters space. On the constant heat duty basis, the pumping power has been reduced up to 47% for the combined enhancement geometry than the individual enhancement geometries. However, full-length and short-length twisted-tapes with oblique teeth in combination with axial corrugations show only marginal improvements over the twisted-tapes without oblique teeth.     

Experimental investigation on the flow instability behavior of a multi-channel boiling natural circulation loop at low-pressures

Natural circulation as a mode of heat removal is being considered as a prominent passive feature in the innovative nuclear reactor designs, particularly in boiling-water-reactors, due to its simplicity and economy. However, boiling natural circulation system poses many challenges to designer due to occurrence of various kinds of instabilities such as excursive instability, density wave oscillations, flow pattern transition instability, geysering and metastable states in parallel channels. This problem assumes greater significance particularly at low-pressures i.e. during startup, where there is great difference in the properties of two phases. In light of this, a parallel channel loop has been designed and installed that has a geometrical resemblance to the pressure-tube-type boiling-water-reactor, to investigate into the behavior of boiling natural circulation. The loop comprises of four identical parallel channels connected between two common plenums i.e. steam drum and header. The recirculation path is provided by a single downcomer connected between steam drum and header. Experiments have been conducted over a wide range of power and pressures (1–10 bar). Two distinct unstable zones are observed with respect to power i.e. corresponding to low power (Type-I) and high power (Type-II) with a stable zone at intermediate powers. The nature of oscillations in terms of their amplitude and frequency and their evolution for Type-I and Type-II instabilities are studied with respect to the effect of heater power and pressure. This paper discusses the evolution of unstable and stable behavior along with the nature of flow oscillation in the channels and the effect of pressure on it.