Discrete π Stack of a Tweezer-Shaped Naphthalenediimide–Anthracene Conjugate

The design and synthesis of a tweezer-shaped naphthalenediimide (NDI)–anthracene conjugate ( 2NDI ) are reported. In the structure of the closed form (π_NDI ⋅⋅⋅ π_NDI stack) of 2NDI , which was elucidated by single-crystal XRD, the existence of C−H ⋅⋅⋅ O hydrogen bonding involving the nearest carbonyl oxygen atom of an NDI unit was suggested. The tunability of π_NDI ⋅⋅⋅ π_NDI interactions was studied by means of UV/Vis absorption, fluorescence and NMR spectroscopy and molecular modelling. This revealed that the π_NDI ⋅⋅⋅ π_NDI interactions in 2NDI affect the absorption and emission properties depending on the temperature. Furthermore, in polar solvents, 2NDI prefers the stronger π_NDI ⋅⋅⋅ π_NDI stack, whereas the π_NDI ⋅⋅⋅ π_NDI interaction is diminished in nonpolar solvents. Importantly, the conformational variations of 2NDI can be reversibly switched by variation in temperature, and this suggests potential application for fluorogenic molecular switches upon temperature changes.     

Nucleophilic additions of primary and secondary amines to pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

The crystal structures of three compounds formedvia nucleophilic attack of a heterocyclic secondary amine on PCU-8,11-dione, with the concomitant intramolecular attack of one keto oxygen on the carbon of the other ketone, are presented. In all three compounds, the bridging oxygen contains substantial p-character, and the bonds to the attacking nitrogen are significantly shorter than would be expected.     

Strained tridecane cage systems

Hexacyclo[6.5.0.0^2,7.0^4,12.0^5,10.0^9.13]tridecane (HCTD) contains two four-membered, two five-membered and two six-membered rings fused into a cage structure which contains about 77.0 kcal/mol of strain energy. Attempts to prepare the thioketal from the diketone of HCTD led to a skeletal rearrangement to produce a cage with one four-membered, four five-membered, and two six-membered rings fused into a cage (RHCTD). The corresponding RHCTD hydrocarbon has a strain energy 13.7 kcal/mol less than that of the starting tridecane (HCTD) which provides the driving force for the rearrangement. The X-ray structures of two HCTD derivatives and one RHCTD derivative are reported. The bond lengths in the three reported structures are normal for cages of this type. The structure of tetracyclo[6.3.0.0^3,7.0^4,11]undecane-5,10-dione mono(ketene 1,3-propanedithioacetal) is discussed also.     

CPMD/GULP QM/MM interface for modeling periodic solids: Implementation and its application in the study of Y‐zeolite supported Rhn clusters

We report here the development of hybrid quantum mechanics/molecular mechanics (QM/MM) interface between the plane‐wave density functional theory based CPMD code and the empirical force‐field based GULP code for modeling periodic solids and surfaces. The hybrid QM/MM interface is based on the electrostatic coupling between QM and MM regions. The interface is designed for carrying out full relaxation of all the QM and MM atoms during geometry optimizations and molecular dynamics simulations, including the boundary atoms. Both Born–Oppenheimer and Car–Parrinello molecular dynamics schemes are enabled for the QM part during the QM/MM calculations. This interface has the advantage of parallelization of both the programs such that the QM and MM force evaluations can be carried out in parallel to model large systems. The interface program is first validated for total energy conservation and parallel scaling performance is benchmarked. Oxygen vacancy in α‐cristobalite is then studied in detail and the results are compared with a fully QM calculation and experimental data. Subsequently, we use our implementation to investigate the structure of rhodium cluster (Rh_n; n = 2 to 6) formed from Rh(C₂H₄)₂ complex adsorbed within a cavity of Y‐zeolite in a reducible atmosphere of H₂ gas. © 2016 Wiley Periodicals, Inc.     

Robust Stability and Performance Analysis of Uncertain Systems Using Linear Matrix Inequalities

A wide variety of problems in system and control theory can be formulated or reformulated as convex optimization problems involving linear matrix inequalities (LMIs), that is, constraints requiring an affine combination of symmetric matrices to be positive semidefinite. For a few very special cases, there are analytical solutions to these problems, but in general LMI problems can be solved numerically in a very efficient way. Thus, the reduction of a control problem to an optimization problem based on LMIs constitutes, in a sense, a solution to the original problem. The objective of this article is to provide a tutorial on the application of optimization based on LMIs to robust control problems. In the first part of the article, we provide a brief introduction to optimization based on LMIs. In the second part, we describe a specific example, that of the robust stability and performance analysis of uncertain systems, using LMI optimization.     

Neuroprotective Ability of Apocynin Loaded Nanoparticles (APO-NPs) as NADPH Oxidase (NOX)-Mediated ROS Modulator for Hydrogen Peroxide-Induced Oxidative Neuronal Injuries

Apocynin (APO) is a known multi-enzymatic complexed compound, employed as a viable NADPH oxidase (NOX) inhibitor, extensively used in both traditional and modern-day therapeutic strategies to combat neuronal disorders. However, its therapeutic efficacy is limited by lower solubility and lesser bioavailability; thus, a suitable nanocarrier system to overcome such limitations is needed. The present study is designed to fabricate APO-loaded polymeric nanoparticles (APO-NPs) to enhance its therapeutic efficacy and sustainability in the biological system. The optimized APO NPs in the study exhibited 103.6 ± 6.8 nm and −13.7 ± 0.43 mV of particle size and zeta potential, respectively, along with further confirmation by TEM. In addition, the antioxidant (AO) abilities quantified by DPPH and nitric oxide scavenging assays exhibited comparatively higher AO potential of APO-NPs than APO alone. An in-vitro release profile displayed a linear diffusion pattern of zero order kinetics for APO from the NPs, followed by its cytotoxicity evaluation on the PC12 cell line, which revealed minimal toxicity with higher cell viability, even after treatment with a stress inducer (H₂O₂). The stability of APO-NPs after six months showed minimal AO decline in comparison to APO only, indicating that the designed nano-formulation enhanced therapeutic efficacy for modulating NOX-mediated ROS generation.     

Physics beyond Standard Model: Working group 3 report

This is a summary of the beyond the Standard Model (including model building) working group of the WHEPP-X workshop held at Chennai from January 3 to 15, 2008. Participants: Neelima Agarwal, S K Agarwalla, C S Aulakh, A Belyaev, S S Biswal, B Bhattacharjee, G Bhattacharyya, L Calibbi, D Choudhury, E J Chun, D Das, A De Roeck, N G Deshpande, E Dudas, A Giri, D Grellshceid, R Godbole, S Goswami, M Guchait, M Hirsch, R Kaul, B Kodrani, M C Kumar, A Kundu, Y Mambrini, P Mathews, B Mellado, R Mohanta, S Mohanty, A Nyffeler, S Pakvasa, M K Parida, M Passera, C Petridou, S Poddar, P Poulose, A Rajaraman, G Rajasekaran, V Ravindran, Kumar Rao, D P Roy, Probir Roy, K A Saheb, V H Satheeshkumar, T Schwetz, A Tripathi, R Vaidya and S Vempati