ChemInform Abstract: Gold Oxyfluorides,Au(OF)n (n = 1—6): Novel Superhalogens with Oxyfluoride Ligands.

Applying gradient corrected DFT (Gaussian 09 program) with the gradient corrected hybrid form of exchange‐correlation potentials B3LYP, Au(OF)_n complexes (n = 1—6) and their anions are systematically studied.     

Photomagnetic and nonlinear optical properties in cis‐trans green fluoroprotein chromophore coupled Bis‐imino nitroxide diradicals

The current study extends an earlier investigation (Bhattacharya, et al., Phys. Chem. Chem. Phys. 2012, 14, 6905) to further explore various photomagnetic and optical properties of bis‐imino nitroxide, that is, (IN)₂‐based green fluorescent protein (GFP) chromophore coupled diradicals revealing new significant features. The conversion mechanisms of selected trans‐isomers into their corresponding cis‐conformers are discussed in detailed using a number of recently‐developed density functional theory (DFT) functionals based on the Minnesota suite of DFT‐models as well as using some other DFT functionals developed earlier. To provide a more in‐depth analysis of variations in magnetic properties as trans‐conformers (singlet ground‐state) convert into their cis‐analogues (triplet ground‐state), the changes in exchange magnetic coupling constants J are compared with the variation of the selected aromaticity indices. The aromaticity indices include the nuclear independent chemical shift [NICS(0)] values calculated at the center of ring structures and the harmonic oscillator model of aromaticity. Furthermore, the investigation of static nonlinear optical response properties in the (IN)₂‐based GFP chromophore coupled diradicals reveal unusually large static first hyperpolarizabilities for these systems which is highly significant for practical applications in optics and optoelectronics. © 2015 Wiley Periodicals, Inc.     

Competition between alkalide characteristics and nonlinear optical properties in OLi3MLi3O (M = Li,Na, and K) complexes

Alkalides possess enhanced nonlinear optical (NLO) responses due to localization of excess electrons on alkali metals. Employing MP2/6‐311 + G(d) level, we design novel alkalides by placing alkali atoms (M) between two Li₃O superalkalis. We notice a competition between alkalide characteristics and NLO properties in OLi₃? M? Li₃O (M = Li, Na, and K) isomers. For instance, the atomic charge on M (q _M) in D _2h structure is ?0.58e for M = Li and its first static mean hyperpolarizablity (β _o) is 1 a.u., but in C _2v structure, q _M = ?0.12e and β _o= 3.4 × 10³ a.u. More interestingly, the β _o value for M = K (C _2v) increases to 1.9 × 10⁴ a.u. in which q _M = 0.24e . These findings may provide new insights into the design of alkalides, an unusual class of salts and consequently, lead to further researches in this direction.     

An injectable and biomimetic multi‐phase nanocomposite for non‐invasive bone tissue engineering: fabrication and mechanistic evaluation

An injectable, non‐hardening nanocomposite bone graft has been developed using a combination of nanohydroxyapatite as bioactive and osseointegrative material; P‐15 peptide‐modified poly(lactic‐co‐glycolic acid) (PLGA) microspheres as biomimetic and osteoinductive agent; and PLGA–poly(ethylene glycol) (PEG)–PLGA as a carrier gel. Increase in lactic acid/glycolic acid ratio of PLGA–PEG–PLGA resulted in stronger gels with a wider gelation window. Addition of 2.5‐fold nanohydroxyapatite resulted in significant changes in injectability (3.5‐fold force of injection), swelling characteristics (2.5 times swelling index), rheological (shear viscosity from 2.1 × 10¹ Pa s for NC3_700 to 1.5 × 10⁶ Pa s for NC3_73.52 and from 3.9 × 10² Pa s for NC8_700 to 3.76 × 10⁶ Pa s for NC8_732; an increase in elasticity at the level of 1–1000 kPa), and thermal properties of the nanocomposites. A mechanistic study showed that nanohydroxyapatite exhibits a high degree of association with the gel and interferes with its gelation owing to changes in hydrogen bonding interactions between C=?O of polymer chains and P–OH groups of nanohydroxyapatite with water molecules of the gel. A schematic was developed demonstrating changes in bonding interactions among constituent phases with respect to nanohydroxyapatite content emphasizing the importance of material interactions while fabricating multi‐phase nanocomposites for various biomedical applications. Copyright © 2017 John Wiley & Sons, Ltd.     

Pharmacophore modelling,atom-based 3D-QSAR generation and virtual screening of molecules projected for mPGES-1 inhibitory activity

COX-2 inhibitors exhibit anticancer effects in various cancer models but due to the adverse side effects associated with these inhibitors, targeting molecules downstream of COX-2 (such as mPGES-1) has been suggested. Even after calls for mPGES-1 inhibitor design, to date there are only a few published inhibitors targeting the enzyme and displaying anticancer activity. In the present study, we have deployed both ligand and structure-based drug design approaches to hunt novel drug-like candidates as mPGES-1 inhibitors. Fifty-four compounds with tested mPGES-1 inhibitory value were used to develop a model with four pharmacophoric features. 3D-QSAR studies were undertaken to check the robustness of the model. Statistical parameters such as r² = 0.9924, q² = 0.5761 and F test = 1139.7 indicated significant predictive ability of the proposed model. Our QSAR model exhibits sites where a hydrogen bond donor, hydrophobic group and the aromatic ring can be substituted so as to enhance the efficacy of the inhibitor. Furthermore, we used our validated pharmacophore model as a three-dimensional query to screen the FDA-approved Lopac database. Finally, five compounds were selected as potent mPGES-1 inhibitors on the basis of their docking energy and pharmacokinetic properties such as ADME and Lipinski rule of five.     

Order-N Formulation and Dynamics of Multi-Unit Flexible Space Manipulators

As robotic manipulators gain more importance in space operations, it is becoming imperative to understand their distinctive dynamics and control characteristics. With the increasing complexity of space robots, efficient algorithms are now required for their simulation. The present study uses an order-N algorithm, based on the Lagrangian approach and velocity transformations, to simulate the planar dynamics of a novel orbiting manipulator with arbitrary number of slewing and deployable flexible links. The relatively general formulation accounts for interactions between orbital, librational, slewing, deployment, and vibrational degrees of freedom, and thus is applicable to a large class of manipulator systems of contemporary interest. A parametric analysis of the system dynamics is carried out to investigate the effects of initial disturbances, variation of system parameters and maneuver profiles. The study suggests significant coupling between the rigid body motion and structural vibrations. As a result, the system's flexibility can significantly affect the manipulator's performance.     

Effects of suction or blowing on the velocity and temperature distribution in the flow past a porous flat plate of a power-law fluid

An analysis is made of the steady flow of a non-Newtonian fluid past an infinite porous flat plate subject to suction or blowing. The incompressible fluid obeys Ostwald-de Waele power-law model. It is shown that steady solutions for velocity distribution exist only for a pseudoplastic (shear-thinning) fluid for which the power-law index n satisfies 0<n<1 provided that there is suction at the plate. Velocity at a point is found to increase with increase in n. No steady solution for velocity distribution exists when there is blowing at the plate. The solution of the energy equation governing temperature distribution in the flow of a pseudoplastic fluid past an infinite porous plate subject to uniform suction reveals that temperature at a given point near the plate increases with n but further away, temperature decreases with increase in n. A novel result of the analysis is that both the skin-friction and the heat flux at the plate are independent of n.     

Chemically Orthogonal Three‐Patch Microparticles

Compared to two‐dimensional substrates, only a few methodologies exist for the spatially controlled decoration of three‐dimensional objects, such as microparticles. Combining electrohydrodynamic co‐jetting with synthetic polymer chemistry, we were able to create two‐ and three‐patch microparticles displaying chemically orthogonal anchor groups on three distinct surface patches of the same particle. This approach takes advantage of a combination of novel chemically orthogonal polylactide‐based polymers and their processing by electrohydrodynamic co‐jetting to yield unprecedented multifunctional microparticles. Several micropatterned particles were fabricated displaying orthogonal click functionalities. Specifically, we demonstrate novel two‐ and three‐patch particles. Multi‐patch particles are highly sought after for their potential to present multiple distinct ligands in a directional manner. This work clearly establishes a viable route towards orthogonal reaction strategies on multivalent micropatterned particles.