Different Types of Nickel,Cobalt, and Manganese Complexes originating from 2‐Imidazolecarboxaldiimine of Triethylenetetraamine

The reactivity of the 2‐imidazolecarboxaldiimine of triethylenetetraamine (H2imida) towards divalent manganese, cobalt, and nickel ions differs. It forms a cationic nickel(II) complex by acting as a hexa‐dentate ligand, whereas the cobalt(II) complex formation took place by deprotonation of the H2imida forming a neutral complex with imida. Deprotonation of the ligand by H2imida by cobalt(II) ions caused quenching of the fluorescence emission at 312 nm, such a quenching effect was not observed with the nickel ions. On the other hand, a mononuclear manganese(II) complex of a new tetradentate ligand was formed by manganese(II) assisted intramolecular cyclization reactions of H2imida.     

Theoretical insight of nitric oxide adsorption on neutral and charged Pdn (n = 1–5) clusters

Density functional theory (DFT) calculations within the framework of generalized gradient approximation have been used to systematically investigate the adsorption of nitric oxide (NO) molecule on neutral, cationic, and anionic Pd_n (n = 1–5) clusters. NO coordinate to one Pd atom of the cluster by the end‐on mode, where the tilted end‐on structure is more favorable due to the additional electron in the π* orbital. On the contrary, in the neutral and cationic Pd₂ system, NO coordinates to the bridge site of cluster preferably by the side‐on mode. Charge transfer between Pd clusters and NO molecule and the corresponding weakening of N? O bond is an essential factor for the adsorption. The N? O stretching frequency follow the order of cationic > neutral > anionic. Binding energy of NO on anionic clusters is found to be greater than those of neutral and cationic clusters. © 2015 Wiley Periodicals, Inc.     

QM/MM Studies on Cyclodextrin-Alcohol Interaction

The main objective of this study is to provide an insight into the interactions involved during adsorption of the alcohols on β-CD composite nanostructured membrane. Interactions between β-cyclodextrin (β-CD) and alcohols (methanol, ethanol and butanol) are studied using the QM/MM method. Magnitude of interaction energies show that the alcohols are adsorbed on the membrane. In addition, the thermochemical analysis suggests that the formation of these host-guest complexes is enthalpy driven.     

A comparison of the effect of nanotube chirality and electronic properties on the π–π interaction of single‐wall carbon nanotubes with pyrazinamide antitubercular drug

Theoretical investigation on local electronic structure and stability of the π–π stacking interaction of pyrazinamide (PZA) with armchair (5,5) and zigzag (9,0) single‐walled carbon nanotubes (SWCNTs) is performed using density functional theory (DFT). PZA is physisorbed onto nanotube sidewall through interaction of π orbitals of PZA and SWCNT and the enhanced structural stability of PZA/SWCNT systems is due to weak side‐on rather than the head‐on π‐interactions. The physisorption of PZA onto SWCNT sidewall is thermodynamically favored; as a consequence, it modulates the electronic properties of pristine nanotube in the vicinity of Fermi region and π–π stacked interactions is stronger in (9,0) SWCNT compared to (5,5) SWCNT. The density of states (DOS) analysis show that PZA contributes toward the enhancement of electronic states. Projected DOS and frontier orbital analysis in the vicinity of Fermi level region suggest the electronic states to be contributed from SWCNT rather than PZA. In addition, hybrid DFT calculation which includes the dispersion correction is employed to explain the non‐covalent π–π stacking interaction between PZA and SWCNT. The local density approximation and GGA results are compared with DFT‐D to explain near about accurately the weak nonbonded van der Waals interactions between PZA and SWCNTs. © 2012 Wiley Periodicals, Inc.     

Analysis of electron energy distribution function in a magnetically filtered complex plasma

The electron energy distribution function (EEDF) for a magnetically filtered dusty plasma is studied in a dusty double plasma device where the electron energy can be varied from 0.15 eV to ～ 2.8 eV and plasma density from 10 6 cm-3 to 10 9cm-3 . The characteristics of EEDF for these ranges of plasma parameters are investigated in a pristine plasma as well as in a dusty plasma. The results show that in the presence of dust, there is a drastic modification in EEDF patterns in a plasma with higher electron temperature and density than those in a low temperature and low density plasma produced by the magnetic filter.     

Mixed ionic and electronic conductivity study of charge transfer complexes of some substituted pyridines with iodine monochloride (ICl) by AC impedance spectroscopy

Mixed ionic and electronic conductivity of three solid charge transfer (CT) complexes of pyridine, 4-methylpyridine (γ-picoline) and 3,5-dimethylpyridine (3,5-lutidine) with ICl (iodine monochloride) are reported. Electrical parameters of the prepared complexes in the pellet form are evaluated at various temperatures and at wide frequency range by employing AC complex impedance spectroscopic technique. Suitable equivalent circuits for the Nyquist plots, which provide the most realistic model of the electrical properties of the CT complexes, have been suggested. Both transport number measurements and impedance spectra reveal that the conduction in γ-picoline-ICl complex is mainly due to ions, in 3,5-dimethylpyridine-ICl complex, it is due to both ions and electrons and in pyridine-ICl complex, it is predominantly due to electrons. The a.c. conductivity measurements of the CT complexes have been carried out in the frequency range of 10–10⁵ Hz within the temperature range of 303–353 K. The variation of a.c. conductivity with frequency follows the Jonscher’s universal power law. The temperature dependence of electrical conductivity suggests the semiconducting behaviour of the materials.     

Ab initio study on the noncovalent adsorption of camptothecin anticancer drug onto graphene, defect modified graphene and graphene oxide

The application of graphene and related nanomaterials like boron nitride (BN) nanosheets, BN-graphene hybrid nanomaterials, and graphene oxide (GO) for adsorption of anticancer chemotherapeutic camptothecin (CPT) along with the effect on electronic properties prior to functionalization and after functionalization has been reported using density functional theory (DFT) calculations. The inclusion of dispersion correction to DFT is instrumental in accounting for van der Waals π–π stacking between CPT and the nanomaterial. The adsorption of CPT exhibits significant strain within the nanosheets and noncovalent adsorption of CPT is thermodynamically favoured onto the nanosheets. In case of GO, surface incorporation of functional groups result in significant crumpling along the basal plane and the interaction is basically mediated by H-bonding rather than π–π stacking. Docking studies predict the plausible binding of CPT, CPT functionalized graphene and GO with topoisomerase I (top 1) signifying that CPT interacts through π stacking with AT and GC base pairs of DNA and in presence of nano support, DNA bases preferentially gets bound to the basal plane of graphene and GO rather than the edges. At a theoretical level of understanding, our studies point out the noncovalent interaction of CPT with graphene based nanomaterials and GO for loading and delivery of anticancer chemotherapeutic along with active binding to Top1 protein.