A Tale of Biphenyl and Terphenyl Substituents for Structurally Diverse Ketiminato Magnesium,Calcium and Germanium Complexes

In this paper, we have used two N,O‐ketiminato ligands ( L1 and L2 ) with biphenyl and terphenyl substituent on the nitrogen atom. Deprotonation of L1 with KN(SiMe₃)₂ and subsequent reaction with MgI₂ led to a homoleptic dinuclear magnesium complex ( 1 ) with a Mg₂O₂ four‐membered ring. Deprotonation with nBuLi and subsequent reaction with MgI₂ afforded a unusual dinuclear magnesium complex ( 2 ) with a Mg₂O₂ ring. Extension of the ligand for calcium resulted in a trinuclear calcium complex ( 3 ) with six four‐membered Ca₂O₂ rings. We could not isolate any chelating complex when L2 was used as a ligand, and only oxygen bound magnesium ( 4 ) and calcium ( 5 ) adducts were isolated. DFT studies were performed to understand this dissimilar behavior. More diverse results were obtained when lithiated L1 and L2 were treated with germanium dichloride. We were able to stabilize a monomeric germylene monochloride ( 7 ) with L1 . However, with L2 , an unusual ligand scrambling, and a C?C coupling take place, leading to the formation of a secondary carbocation with GeCl₃‐ as a counter‐anion ( 8 ). Besides, a germanium dichloride adduct ( 9 ) bound to the oxygen center of the ligand was obtained as the minor product.     

Microwave-assisted rapid and efficient synthesis of chromene-fused pyrrole derivatives through multicomponent reaction and evaluation of antibacterial activity with molecular docking investigation

The current study aimed to identify a new strategy of FeCl₃ catalyzed multicomponent synthesis of substituted 2H-chromene–fused pyrrole derivatives. A series of chromene-based pyrrole prepared by employing an array of 3-nitro-2H-chromenes, aniline, and acetylacetone in toluene under microwave irradiation. Using FeCl₃ as a prompt catalyst and microwave irradiation to synthesize 2H-chromene–fused pyrrole motifs significantly reduces the reaction time and facilitates to high yields (83%-95%). Structure of all synthesized compounds analyzed by spectroscopic analysis. One-pot reaction, short reaction period, and simple experimental procedure are the fascinating properties associated with this protocol. The in vitro antibacterial activity of the entire series was assessed against Staphylococcus aureus and Escherichia coli. Out of all the compounds, 15b and 15h revealed most excellent potency against both the bacterial strains relative to the reference gentamicin. Docking study was employed to determine the possible binding orientation of DNA gyrase with the active sites of chromene-fused pyrrole analog. The docking results show that compounds 15b and 15h have higher binding affinity with energy −8.00 and −8.80 kcal/mol. These results illuminate the mode of binding progression and provide an esteemed pathway for the design and the structural modification of chromene-fused pyrroles as a newly advanced class of antibacterial agent.     

Theoretical investigations of the gas phase reaction of limonene (C10H16) with OH radical

The rate coefficients of hydroxyl radical (OH) reaction with limonene were computed using canonical variational transition state theory with small-curvature tunnelling between 275 and 400 K. The geometries and frequencies of all the stationary points are calculated using hybrid density functional theory methods M06-2X and MPWB1K with 6-31+G(d,p), 6-311++G(d,p), and 6-311+G(2df,2p) basis sets. Both addition and abstraction channels of the title reaction were explored. The rate coefficients obtained over the temperature range of 275–400 K were used to derive the Arrhenius expressions: k(T) = 4.06×10^?34 T^7.07 exp[4515/T] and k(T) = 7.37×10^?25 T^3.9 exp[3169/T] cm³ molecule^?1 s^?1 at M06-2X/6-311+G(2df,2p) and MPWB1K/6-311+G(2df,2p) levels of theory, respectively. Kinetic study indicated that addition reactions are major contributors to the total reaction in the studied temperature range. The atmospheric lifetime (τ) of limonene due to its reactions with various tropospheric oxidants was calculated and concluded that limonene is lost in the atmosphere within a few hours after it is released. The ozone production potential of limonene was computed to be (14–18) ppm, which indicated that degradation of limonene would lead to a significant amount of ozone production in the troposphere.     

On the application of the two-level large-eddy simulation method to turbulent free-shear and wake flows

We present application of the hybrid two-level large-eddy simulation (TLS-LES) method, a multi-scale simulation model, to turbulent free-shear and wake flows at moderately high Reynolds number. The TLS-LES method combines the scale-separation-based two-level simulation (TLS) model with the spatial-filtering-based conventional large-eddy simulation (LES) model in an additive manner using a normalised blending function. The additive blending can be performed in a static or a dynamic manner. We demonstrate that the method, which has been originally developed for wall-bounded flows, can be used to simulate flows in complex configurations without requiring any further adjustments to the model. In this study, three canonical flows are simulated, which are representative of free-shear and wake flows. These cases include a temporally evolving mixing layer, flow past a circular cylinder in a uniform flow and flow past a finite-span airfoil placed in a uniform flow at three different angle of attacks. We analyse the role of static and dynamic blending functions, large-scale grid resolution and the effect of small scales on the instantaneous flow features and turbulence statistics. The results obtained from these cases demonstrate robustness, accuracy and consistency of the multi-scale TLS-LES method and show that the method is suitable for investigation of turbulent flows that encompass features such as massive separation, reattachment, transition to turbulence and unsteady wake, which are challenging to model numerically.     

Identity orientation of complete bipartite graphs

An identity orientation of a graph G=(V,E) is an orientation of some of the edges of E such that the resulting partially oriented graph has no automorphism other than the identity. We show that the complete bipartite graph K_s,t, with st, does not have an identity orientation if t3^s-log₃(s-1). We also show that if (r+1)(r+2)2s then K_s,3^s-r does have an identity orientation. These results improve the previous bounds obtained by Harary and Jacobson (Discuss. Math. - Graph Theory 21 (2001) 158). We use these results to determine exactly the values of t for which an identity orientation of K_s,t exists for 2s17.     

Through‐Space 1,4‐Palladium Migration and 1,2‐Aryl Shift: Direct Access to Dibenzo[a,c]carbazoles through a Triple CH Functionalization Cascade

A palladium‐catalyzed expeditious synthesis of dibenzofused carbazoles from readily available 2‐arylindoles and diaryliodonium salts is reported. Interestingly, after the electrophilic C3 palladation of indole, an unexpected “through‐space” 1,4‐palladium migration to the 2‐aryl moiety, by remote C?H bond activation followed by C?H arylation with diaryliodonium salt, and an unprecedented 1,2‐aryl shift take place. Finally, an intramolecular cross‐dehydrogenative coupling (CDC) at the C2 position affords dibenzo[a,c]carbazoles in high yields. Remarkably, the present migratory annulation occurs through three C?H bond activation one C?C bond cleavage, and the simultaneous construction of three new C?C bonds in a single operation.     

Colloidal,Functional, Piezoelectric BaTiO3-Au Nanohybrid for Wireless Cell Therapy

Ultrasound-assisted reactive oxygen species (ROS) generation from piezoelectric nanomaterial offers unique wireless therapeutic approach in remote places. In the previous work, piezoelectric barium titanate (BaTiO₃) nanorod have been synthesized and used for wireless cell therapy. However, the piezoelectric property of BaTiO₃ nanorod needs further improvement for diverse applications. In this work, it is shown that gold nanoparticle conjugation with BaTiO₃ nanorod (BaTiO₃-Au) can significantly enhance the piezoelectric performance with the piezoelectric constant value of 110 pm V⁻¹. The colloidal BaTiO₃-Au is further functionalized with folate for selective targeting of folate-overexpressed cancer cells and used for wireless cell therapy via intracellular ROS generation under ultrasound exposure. The synthesized colloidal nanohybrid can be used for various therapeutic applications.     

Microstrip patch array antenna on photonic crystal substrate at terahertz frequency

Recent advancement in the fabrication and packaging technology has led to the micrometer and nanometer-scale device modeling. This technological development and subsequent reduction in the dimension of devices like modulators, detectors and antennas has brought a thought of increasing the operating frequency of the system to the extent of sub-millimeter wavelength. In the view of the technical breakthrough in the area of fabrication and packaging, we have explored a printed antenna array on the photonic crystal in the terahertz spectrum in this paper. An equivalent circuit model of the antenna has been proposed and a methodology to investigate various electrical parameters is discussed. Tunable parameters of the structure have been explored to optimize the electrical performance of the proposed antenna. The analysis is also compared by using two simulators: (a) CST Microwave Studio based on finite integral technique and (b) Ansoft HFSS based on finite element method. The effect of the photonic crystal as substrate to enhance the gain of this kind of the antenna has also been demonstrated. The gain, directivity, front-to-back ratio (F/B ratio), and the radiation efficiency of the proposed antenna at 600 GHz is 16.88 dBi, 17.19 dBi, 14.77 dB and 89.72%, respectively. Finally, the performance of the antenna has been compared with the reported literature.