Studies on α-, β-, and γ-cyclodextrin inclusion complexes of isoquinoline alkaloids berberine, palmatine and coralyne

The complexation of three isoquinoline alkaloids berberine, palmatine and coralyne with α-, β-, and γ-CDs were studied by absorption, fluorescence, circular dichroism, NMR spectroscopy and microcalorimetric assay techniques. Their binding constant (K _BH) values were determined by Benesi–Hildebrand equation. All the alkaloids formed 1:1 stoichiometry complexes with the cyclodextrins (CDs). The binding affinity is largest in β-CD followed by γ-, and α-CD for coralyne, followed by berberine and then palmatine. The thermodynamic parameters of the complexation were determined by calorimetry. The stoichiometry of complex formation and the variation of the apparent binding constant from spectroscopic studies were confirmed by calorimetry. The formation of the inclusion complexes was entropy driven in almost all the systems. Coralyne formed the strongest complex with all the CDs, followed by berberine and palmatine in that order. Coralyne-β-CD complex was studied through NMR, indicating more than one interaction mode.     

Supramolecular self-assembly and nanoencapsulation of [60]fullerene by bis-β-cyclodextrin

Bis-β-cyclodextrin connected via ethylene diamine on the primary side of the β-cyclodextrin was synthesized and used for the supramolecular non-covalent inclusion complex with C₆₀ in a mixed solvent system at room temperature. The apparent association constant of the 2:2 inclusion complex determined by combination of UV–Vis absorbance and Benesi–Hildebrand equation was found to be 1.78 × 10⁶ M^?1. The product obtained was highly water-soluble and superior in stability in aqueous medium as compared to previously known β-cyclodextrin/C₆₀ complex. The non-covalent self-assembly of bis-β-cyclodextrin and C₆₀ was characterized and confirmed from FT-IR, UV–Vis, XRD and TGA. The supramolecular aggregation behavior and particle size of the inclusion complex was found from transmission electron microscope and static light scattering measurements. The size of the inclusion complex was found to be ~30 ± 5 nm.     

Microwave sintering of nickel ferrite nanoparticles processed via sol–gel method

Magnetic nickel ferrite (NiFe₂O₄) was prepared by sol–gel process and calcined in the 2.45 GHz singlemode microwave furnace to synthesize nickel nanopowder. The sol–gel method was used for the processing of the NiFe₂O₄ powder because of its potential for making fine, pure and homogeneous powders. Sol–gel is a chemical method that has the possibility of synthesizing a reproducible material. Microwave energy is used for the calcining of this powder and the sintering of the NiFe₂O₄ samples. Its use for calcination has the advantage of reducing the total processing time and the soak temperature. In addition to the above combination of sol–gel and microwave processing yields to nanoscale particles and a more uniform distribution of their sizes. X-ray diffraction, energy dispersive X-ray spectroscopy, transmission electron microscopy and vibrating sample magnetometer were carried out to investigate structural, elemental, morphological and magnetic aspects of NiFe₂O₄. The results showed that the mean size and the saturation magnetization of the NiFe₂O₄ nanoparticles are about 30 nm and 55.27 emu/g, respectively. This method could be used as an alternative to other chemical methods in order to obtain NiFe₂O₄ nanoparticles.     

Role of graphene in structural transformation of zirconium oxide

Fine powders of zirconium oxide (ZrO₂) were prepared using zirconium oxychloride by combustion method. The crystalline size of pure ZrO₂ was in range of 14–45 nm. Graphene was incorporated in ZrO₂ using graphene oxide as precursor and reducing it with hydrazine hydrate. X-Ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analysis and Raman spectroscopy methods were used to characterize the samples. The role of graphene in structural transformation of ZrO₂ to monoclinic phase was clearly observed.     

Synthesis of SnO2 nanostructures by ultrasonic-assisted sol–gel method

Fluorine doped SnO₂ nanostructures were grown using ultrasonic assisted sol–gel method. The gel was obtained by dissolving stannous chloride in methanol with ammonium fluoride as dopant followed by irradiation with ultrasonic vibrations. Obtained samples were characterized by structural, morphological and optical studies. All the peaks in the X-ray diffractograms are identified and indexed as tetragonal cassiterite structure. Negative slope of Williamson–Hall plots indicates compressive strain. Particle size of SnO₂ nanostructures is decreases with increases in concentration of fluorine doping. Atomic force microscopy, scanning electron microscopy and transmission electron microscopy studies confirm the formation of ring like porous structures and then hollow tube like growth with increase in the fluorine concentration. Peaks in Raman spectra also indicate strong confinement in SnO₂ particles. Distinct peaks in the PL spectra make the structure suitable for photovoltaic applications.     

Sodium alginate/HPMC/liquid paraffin emulsified (o/w) gel beads,by factorial design approach; and in vitro analysis

The present study involved development of a novel sodium alginate (SA)/HPMC/light liquid paraffin emulsified (o/w) gel beads containing Diclofenac sodium (DS) as an active pharmaceutical ingredient and its site specific delivery by using hard gelatin capsule fabricated by enteric coated Eudragit L-100 polymer. Emulsified gel beads were formulated by 3-level factorial design, ionic gelatin method. The obtained beads were characterized by Fourier transform infrared, X-ray diffraction and Field emission scanning electron microscope analysis. The variables such as SA (X₁), HPMC (X₂), were optimized for drug loading and in vitro drug release with the help of response surface methodology (RSM). The RSM analysis predicted that SA was significant for both drug loading (p = 0.0005) and drug release (p = 0.0041). HPMC was only significant for drug release (p = 0.0154). The cross-product contribution (2FI) and quadratic model were found to be adequate and statistically accurate with correlation value (R²) of 0.9054 and 0.9450 to predict the drug loading and drug release respectively. An increase in concentration of HPMC and SA decreases the drug loading as well as the drug release. The obtained optimum values of drug loading and DS released were 7.43 % and 85.54 % respectively, which were well in agreement with the predicted value by RSM.     

Nickel(II)-Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl-Coenzyme M Reductase

According to the well-accepted mechanism, methyl-coenzyme M reductase (MCR) involves Ni-mediated thiolate-to-disulfide conversion that sustains its catalytic cycle of methane formation in the energy saving pathways of methanotrophic microbes. Model complexes that illustrate Ni-ion mediated reversible thiolate/disulfide transformation are unknown. In this paper we report the synthesis, crystal structure, spectroscopic properties and redox interconversions of a set of Ni^II complexes comprising a tridentate N₂S donor thiol and its analogous N₄S₂ donor disulfide ligands. These complexes demonstrate reversible Ni^II-thiolate/Ni^II-disulfide (both bound and unbound disulfide-S to Ni^II) transformations via thiyl and disulfide monoradical anions that resemble a primary step of MCR's catalytic cycle.     

Stereospecific 1,2-Migrations of Boronate Complexes Induced by Electrophiles

The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2-migration of boronate complexes is driven by displacement of an α-leaving group, oxidation of an α-boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile-induced stereospecific 1,2-migration of groups from boron to sp² and sp³ carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2-migration of boronate complexes: stereospecific Zweifel-type reactions, catalytic conjunctive coupling reactions, and transition metal-free sp²–sp³ couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.     

Effect of Acetonitrile on the Colloidal Behavior of Conventional Cationic Surfactants: A Combined Conductivity,Surface Tension,Fluorescence and FTIR Study

A comprehensive study the effect of acetonitrile (ACN) with four cationic surfactants, viz. tetradecyltrimethylammonium bromide (TTAB), cetyltrimethylammonium bromide (CTAB), cetylpyridinium chloride (CPC) and cetylpyridinium bromide (CPB) was made by using the conductivity, surface tension, fluorescence and FTIR techniques. Significant micellar, interfacial and thermodynamic properties were studied by the tensiometeric and conductivity methods. The critical micelle concentration (CMC), aggregation number (Nagg), and Stern–Volmer constants (Ksv) have also been studied by the steady state fluorescence method using pyrene as probe. The fluorescence study also supports the CMC results obtained from conductivity and surface tension. FTIR was used to ascertain that the strength of intermolecular interactions such as hydrogen bonding, ion–ion pair interactions and induced dipole interactions between the surfactants and ACN depend upon the head-group of the surfactants. The interaction of surfactants with ACN is energetically favorable and occurs via direct interactions between the surfactants and ACN. The results further revealed that the strength of interactions between the surfactants and ACN follows the order: TTAB > CTAB > CPC > CPB.