Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.

Digestive ripening: a synthetic method par excellence for core-shell, alloy, and composite nanostructured materials

The solvated metal atom dispersion (SMAD) method has been used for the synthesis of colloids of metal nanoparticles. It is a top-down approach involving condensation of metal atoms in low temperature solvent matrices in a SMAD reactor maintained at 77 K. Warming of the matrix results in a slurry of metal atoms that interact with one another to form particles that grow in size. The organic solvent solvates the particles and acts as a weak capping agent to halt/slow down the growth process to a certain extent. This as-prepared colloid consists of metal nanoparticles that are quite polydisperse. In a process termed as digestive ripening, addition of a capping agent to the as-prepared colloid which is polydisperse renders it highly monodisperse either under ambient or thermal conditions. In this, as yet not well-understood process, smaller particles grow and the larger ones diminish in size until the system attains uniformity in size and a dynamic equilibrium is established. Using the SMAD method in combination with digestive ripening process, highly monodisperse metal, core-shell, alloy, and composite nanoparticles have been synthesized. This article is a review of our contributions together with some literature reports on this methodology to realize various nanostructured materials.

Synthesis and characterization of nano CoFe2O4 by low‐temperature combustion synthesis using different fuels

The combustion synthesis has been utilized to prepare nanophased powders of cobalt spinel ferrite using ODH and glycine fuels. The product was characterized by X‐ray diffraction; Fourier transformed spectroscopy, scanning electron microscopy, UV‐Vis absorption etc. The XRD patterns reveal spinal cubic structure. SEM profiles show the product is porous, agglomeration, irregular in shape. The crystallite size was estimated using Scherer’s formula and W‐H plots and show nano in size (13 nm: ODH & 36 nm: Glycine). The UV‐Vis absorption shows at ∼430 nm in both the samples.

AN EXPERIMENTAL STUDY ON EFFERVESCENT ATOMIZATION OF BIO-OIL FUELS

This paper presents the work on detailed characterization of effervescent spray of Jatropha and Pongamia pure plant oils. The spray characteristics of these biofuels are compared with those of diesel. Both macroscopic and microscopic spray characteristics at different injection pressures and gas-to-liquid ratio (GLR) have been studied. The particle/droplet imaging analysis (PDIA) technique along with direct imaging methods are used for the purpose of spray characterization. Due to their higher viscosity, pure plant oils showed poor atomization compared to diesel and a blend of diesel and pure plant oil at a given GLR. Pure plant oil sprays showed a lower spray cone angle when compared to diesel and blends at lower GLRs. However, the difference is not significant at higher GLRs. Droplet size measurements at 100 mm downstream of the exit orifice showed reduction in Sauter mean diameter (SMD) diameter with increase in GLR. A radial variation in the SMD is observed for the blend and pure plant oils. Pure oils showed a larger variation when compared to the blend. Spray unsteadiness has been characterized based on the image-to-image variation in the mean droplet diameter and fluctuations in the spray cone angle. Results showed that pure plant oil sprays are more unsteady at lower GLRs when compared to diesel and blend. A critical GLR is identified at which the spray becomes steady. The three regimes of spray operation, namely ``steady spray,'' ``pulsating spray,'' and ``spray and unbroken liquid jet'' are identified in the injection pressure-GLR parameter space for these pure plant oils. Two-phase flow imaging inside the exit orifice shows that for the pure plant oils, the flow is highly transient at low GLRs and the bubbly, slug, and annular two-phase flow regimes are all observed. However, at higher GLRs where the spray is steady, only the annular flow regime is observed.

Molecular Design of Synthetic Benzimidazoles for the Switchover of the Duplex to G-quadruplex DNA Recognition

Benzimidazole derivatives are well known for their antibacterial, antiviral, anticonvulsant, antihistaminic, anthelmintic and antidepressant activities. Benzimidazole's unique base-selective DNA recognition property has been studied widely. However, most of the early benzimidazole systems have been targeted towards the binding of duplex DNA. Here we have shown the evolution and progress of the design and synthesis of new benzimidazole systems towards selective recognition of the double-stranded DNA first. Then in order to achieve selective recognition of the G-quadruplex DNA and utilize their potential as future anti-cancer drug candidates, we have demonstrated their selective cytotoxicity towards the cancer cells and potent telomerase inhibition ability.

Integration of speckle de-noising and image segmentation using synthetic aperture radar image for flood extent extraction

Flood is one of the detrimental hydro-meteorological threats to mankind. This compels very efficient flood assessment models. In this paper, we propose remote sensing based flood assessment using Synthetic Aperture Radar (SAR) image because of its imperviousness to unfavourable weather conditions. However, they suffer from the speckle noise. Hence, the processing of SAR image is applied in two stages: speckle removal filters and image segmentation methods for flood mapping. The speckle noise has been reduced with the help of Lee, Frost and Gamma MAP filters. A performance comparison of these speckle removal filters is presented. From the results obtained, we deduce that the Gamma MAP is reliable. The selected Gamma MAP filtered image is segmented using Gray Level Co-occurrence Matrix (GLCM) and Mean Shift Segmentation (MSS). The GLCM is a texture analysis method that separates the image pixels into water and non-water groups based on their spectral feature whereas MSS is a gradient ascent method, here segmentation is carried out using spectral and spatial information. As test case, Kosi river flood is considered in our study. From the segmentation result of both these methods are comprehensively analysed and concluded that the MSS is efficient for flood mapping.

Fermions in synthetic non-Abelian gauge potentials: rashbon condensates to novel Hamiltonians

Recent advances in the generation of synthetic gauge fields in cold atomic systems have stimulated interest in the physics of interacting bosons and fermions in them. In this paper, we discuss interacting two-component fermionic systems in uniform non-Abelian gauge fields that produce a spin-orbit interaction and uniform spin potentials. Two classes of gauge fields discussed include those that produce a Rashba spin-orbit interaction and the type of gauge fields (SM gauge fields) obtained in experiments by the Shanxi and MIT groups. For high symmetry Rashba gauge fields, a two-particle bound state exists even for a vanishingly small attractive interaction described by a scattering length. Upon increasing the strength of a Rashba gauge field, a finite density of weakly interacting fermions undergoes a crossover from a BCS like ground state to a BEC state of a new kind of boson called the rashbon whose properties are determined solely by the gauge field and not by the interaction between the fermions. The rashbon Bose-Einstein condensate (RBEC) is a quite intriguing state with the rashbon-rashbon interactions being independent of the fermion-fermion interactions (scattering length). Furthermore, we show that the RBEC has a transition temperature of the order of the Fermi temperature, suggesting routes to enhance the transition temperatures of weakly interacting superfluids by tuning the spin-orbit coupling. For the SM gauge fields, we show that in a regime of parameters, a pair of particles with finite centre-of-mass momentum is the most strongly bound. In other regimes of centre-of-mass momenta, there is no two-body bound state, but a resonance like feature appears in the scattering continuum. In the many-body setting, this results in flow enhanced pairing. Also, strongly interacting normal states utilizing the scattering resonance can be created opening the possibility of studying properties of helical Fermi liquids. This paper contains a general discussion of the physics of Feshbach resonance in a non-Abelian gauge field, where several novel features such as centre-of-mass-momentum-dependent effective interactions are shown. It is also shown that a uniform non-Abelian gauge field in conjunction with a spatial potential can be used to generate novel Hamiltonians; we discuss an explicit example of the generation of a monopole Hamiltonian.

Synthetic glutathione peroxidase mimics: effect of nucleophilicity of the aryl thiol cofactor on the antioxidant activity

Catalytic activity of a series of potent amide- and amine-based organoselenium compounds are studied in the presence of various aromatic thiols having electron donating and electron withdrawing substituents on the phenyl ring. This study suggests that the antioxidant activities of the synthetic GPx mimics can be significantly increased by the incorporation of a suitable electron donating group on the phenyl ring of an aromatic thiol.

Flow-enhanced pairing and other unusual effects in Fermi gases in synthetic gauge fields

Recent experiments on fermions in synthetic gauge fields result in systems with a spin-orbit coupling along one spatial axis, a detuning field, and a Zeeman field. We show theoretically that the presence of all three results in interesting and unusual phenomena in a system of interacting fermions (interactions described by a scattering length). For two fermions, bound states appear only over a certain range of the center-of-mass momenta. The deepest bound state appears at a nonzero center-of-mass momentum. For center-of-mass momenta without a bound state, the gauge field induces a resonance-like feature in the scattering continuum resulting in a large scattering phase shift. In the case of many particles, we demonstrate that the system, in a parameter range, shows flow-enhanced pairing, i.e., a Fulde-Farrell-Larkin-Ovchnnikov superfluid state made of robust pairs with a finite center-of-mass momentum. Yet another regime of parameters offers the opportunity to study strongly interacting normal states of spin-orbit-coupled fermionic systems utilizing the resonance-like feature induced by the synthetic gauge field.

Treatment of gray water using anaerobic biofilms created on synthetic and natural fibers

Gray water treatment and reuse is an immediate option to counter the upcoming water shortages in various parts of world, especially urban areas. Anaerobic treatment of gray water in houses is an alternative low cost, low energy and low sludge generating option that can meet this challenge. Typical problems of fluctuating VFA, low pH and sludge washout at low loading rates with gray water feedstock was overcome in two chambered anaerobic biofilm reactors using natural fibers as the biofilm support. The long term performance of using natural fiber based biofilms at moderate and low organic loading rates (OLR) have been examined. Biofilms raised on natural fibers (coir, ridge-gourd) were similar to that of synthetic media (PVC, polyethylene) at lower OLR when operated in pulse fed mode without effluent recirculation and achieved 80-90% COD removal at HRT of 2 d showing a small variability during start-up. Confocal microscopy of the biofilms on natural fibers indicated thinner biofilms, dense cell architecture and low extra cellular polymeric substances (EPS) compared to synthetic supports and this is believed to be key factor in high performance at low OLR and low strength gray water. Natural fibers are thus shown to be an effective biofilm support that withstand fluctuating characteristic of domestic gray water. (C) 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Feshbach resonance in a synthetic non-Abelian gauge field

We study the Feshbach resonance of spin-1/2 particles in a uniform synthetic non-Abelian gauge field that produces spin-orbit coupling and constant spin potentials. We develop a renormalizable quantum field theory including the closed-channel boson which engenders the resonance. We show that the gauge field shifts the Feshbach field where the low-energy scattering length diverges. In addition the Feshbach field is shown to depend on the center-of-mass momentum of the particles. For high-symmetry gauge fields which produce a Rashba spin coupling, we show that the system supports two bound states over a regime of magnetic fields when the background scattering length is negative and the resonance width is comparable to the energy scale of the spin-orbit coupling. We discuss interesting consequences useful for future theoretical and experimental studies, even while our predictions are in agreement with recent experiments.

Fermions in Synthetic Non-Abelian Gauge Fields

Quantum emulation property of the cold atoms has generated a lot of interest in studying systems with synthetic gauge fields. In this article, we describe the physics of two component Fermi gas in the presence of synthetic non-Abelian SU(2) gauge fields. Even for the non-interacting system with the gauge fields, there is an interesting change in the topology of the Fermi surface by tuning only the gauge field strength. When a trapping potential is used in conjunction with the gauge fields, the non-interacting system has the ability to produce novel Hamiltonians and show characteristic change in the density profile of the cloud. Without trap, the gauge fields act as an attractive interaction amplifier and for special kinds of gauge field configurations, there are two-body bound states for any attraction even in three dimensions. For a many body system, the gauge fields can induce a crossover from a weak superfluid to a strong superfluid with transition temperature as high as the Fermi temperature. The superfluid state obtained for a very large gauge field strength is a superfluid of new kind of bosons, called ``rashbons'', the properties of which are independent of its constituent two component fermions and are solely determined by the gauge field strength. We also discuss the collective excitations over the superfluid ground states and the experimental relevance of the physics.

Depalladation of Neutral Monoalkyne- and Dialkyne-Inserted Palladacycles and Alkyne Insertion/Depalladation Reactions of Cationic Palladacycles Derived from N,N `,N `'-Triarylguanidines as Facile Routes for Guanidine-Containing Heterocycles/Carbocycles: Synthetic, Structural, and Mechanistic Aspects

Depalladation of the monoalkyne-inserted cyclopalldated guanidines (kappa 2(C,N)Pd(2,6-Me2C5H3N)Br] (I and II) in PhCl under reflux conditions and that of the dialkyne-inserted cyclopalladated guanidine kappa(2)(C,N):eta(2)(C=C)PdBr] (III) in pyridine under reflux conditions afforded a guanidine-containing indole (1), imidaziondole (2), and benzazepine (3) in 80%, 67%, and 76%, yields, respectively. trans-L2PdBr2] species (L = 2,6-Me2C5H3N, C5H5N) were also isolated in the aforementioned reactions in 35%, 42%, and 40% yields. Further , the reaction of the cyclopalladated guanidine kappa(2)(C,N)Pd(mu-Br)](2) (IV) with AgBF4 in a CH2Cl2/MeCN mixture afforded the cationic pincer type cyclopalladated guanidine kappa(3)(C,N,O)Pd(MeCN)]BF4] (4) in 85% yield and this palladacycle upon crystallization in MeCN and the reaction of kappa(2)(C,N)Pd(mu-Br)](2) (V) with AgBf(4) in a CH2Cl2/MeCN mixture afforded the cationic palladacycles {kappa(2)(C,N)Pd(MeCN)(2)]BF4](5 and 6) in 89% and 91% yields, respectively. The separate reactions of 4 with 2 equiv of methyl phenylpropiolate (MPP) or diphenylacetylene (DPA) and the reaction of 5 with 2 equiv of MPP in PhCl at 110 degrees C afforded the guanidine-containing quinazolinium tetrafluoroborate 7 in 25-32% yields. The reaction of 6 with 2 equiv of DPA under otherwise identical conditions afforded the unsymmetrically substituted guanidinium tetrafluoroborate 8, containing a highly substituted naphthalene unit, in 82% yield. Compounds 1-8 were characterized by analytical and spectroscopic techniques, and all compounds except 4 were characterized by single-crystal X-ray diffraction. The Molecular structure of 2 and 3 are nove, as the framework in the former arises due to the formation of two C-N bonds upon depalladation while the butadienyl unit in the latter revealed cis,cis stereochemistry, a-feature unprecedented in alkyne insertion chemistry. Plausible pathways for the formation of heterocycles/carbocycles are proposed. the influence of substitutents on the aryl rings fo the cyclopalladated guanidine moiety and those on alkynes upon the nature of the products in addressed. Heterocycles 1 and 7 revealed the presence of two rotamers in about a 1.00:0.43 ratio in CDCl3 and in about a 1.00:0.14 ratio in CD3OD, respectively, as detected by H-1 NMR spectroscopy while in CD3CN and DMSO-d(6) (1) and CD3CN and CDCl3 (7), these heterocycles revealed the presence of a single rotamer. These spectral features are attributed to the restricted C-N single-bond rotation of the CN3 unit of the guanidine moiety, which possibly arises from steric constraint due to the formation of a N-H center dot center dot center dot Cl hydrogen bond with CDCl3 (1) and N-H center dot center dot center dot O and O-D center dot center dot center dot O hydrogen bonds with CD3OD (7).

Mixture of Fuels Approach for the Synthesis of SrFeO3-delta Nanocatalyst and Its Impact on the Catalytic Reduction of Nitrobenzene

A modified solution combustion approach was applied in the synthesis of nanosize SrFeO3-delta (SFO) using single as well as mixture of citric acid, oxalic acid, and glycine as fuels with corresponding metal nitrates as precursors. The synthesized and calcined powders were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis and derivative thermogravimetric analysis (TG-DTG), scanning electron microscopy, transmission electron microscopy, N-2 physisorption methods, and acidic strength by n-butyl amine titration methods. The FT-IR spectra show the lower-frequency band at 599 cm(-1) corresponds to metal-oxygen bond (possible Fe-O stretching frequencies) vibrations for the perovskite-structure compound. TG-DTG confirms the formation temperature of SFO ranging between 850-900 degrees C. XRD results reveal that the use of mixture of fuels in the preparation has effect on the crystallite size of the resultant compound. The average particle size of the samples prepared from single fuels as determined from XRD was similar to 50-35 nm, whereas for samples obtained from mixture of fuels, particles with a size of 30-25 nm were obtained. Specifically, the combination of mixture of fuels for the synthesis of SFO catalysts prevents agglomeration of the particles, which in turn leads to decrease in crystallite size and increase in the surface area of the catalysts. It was also observed that the present approach also impacted the catalytic activity of the SFO in the catalytic reduction of nitrobenzene to azoxybenzene.