Biological and catalytic evaluation of Ru(II)‐p‐cymene complexes of Schiff base ligands: Impact of ligand appended moiety on photo‐induced DNA and protein cleavage,cytotoxicity and C‐H activation

Two organometallic Ru(II)‐p‐cymene complexes of the type [Ru(η⁶‐p‐cymene)(L)Cl]PF₆ 1 and 2 , where L is N,N‐bis(4‐isopropylbenzylidene)ethane‐1,2‐diamine (bien, L1 ) or N,N‐bis (pyren‐2‐ylmethylene)ethane‐1,2‐diamine (bpen, L2 ) have been prepared and characterized well. Because of appended pyrenyl groups in coordinated bpen ligand, the complex 2 exhibits higher DNA and protein binding than complex 1 in which isopropylbenzyl groups are incorporated. Interestingly, the luminescent characteristic complex 2 is unique in displaying DNA cleavage after light activation by UVA light at 365 nm through oxygen dependent mechanism. AFM analysis attests the photo‐induced DNA fragmentation ability of complex 2 . Also, the complex 2 cleaves the protein after light exposure in a non‐specific manner suggesting that it can act as a protein photo cleaving agent. In contrast to the trend of DNA and protein interaction of complexes, the complex 1 exhibits cytotoxic activity against human breast carcinoma ( MCF‐7 ) and liver carcinoma ( HepG2 ) with potency higher than that of complex 2 due to enhanced hydrophobicity of isopropyl groups present in p‐cymene and bien ligands. Indeed, complex 2 is inactive against MCF‐7 and HepG2 cancer cell lines even up to 200 μM concentration. The AO/EB staining assay reveals that the complex 1 is able to induce late apoptotic mode of cell death in breast cancer cells, which is further confirmed by inter‐nucleosomal DNA cleavage. Furthermore, the complexes 1 and 2 are evaluated for their catalytic activities and found to be working well for the β‐carboline directed C–H arylation to afford the desired products in good yield (40–47%).     

Reducing the computational cost of NMR crystallography of organic powders at natural isotopic abundance with the help of 13C-13C dipolar couplings

Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed ¹H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using ¹³C-¹³C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although ¹³C-¹³C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.     

High-Throughput Synthesis and Characterization of Aryl Silicones by Using the Piers–Rubinsztajn Reaction

Arylsilicones are widely exploited for their thermal and optical properties. The creation of phenylsilicone elastomers with specific physical properties is typically done by a “one-off” formulation and test process. Herein, it is demonstrated that high-throughput synthesis methods can be used to rapidly prepare a series of arylsilicone elastomers and then the relative impact of different aryl groups on their physical properties is assessed. Aromatic groups were incorporated into polydimethylsiloxane (PDMS) elastomers by exploiting the relative reactivity of different functional groups in the Piers–Rubinsztajn reaction. To analyze trends in the silicone mechanical properties as a function of increasing aryl concentration—structure/property relationships—libraries of elastomers were both quickly synthesized and characterized by using high-throughput suites starting from low viscosity silicone oils/monomers in 96-well plates. Liquid handling parameters were optimized to effectively work with the silicones. Incorporating aryl instead of alkyl crosslinkers into the PDMS backbone increased the silicone elastomer modulus by approximately 50 % (at a crosslink density of 6 %); elastomers prepared with an aromatic crosslinker with three contact points led to much higher moduli compared with those with one contact point at the same crosslink density. When located at precise rather than random points on the silicone chains, diphenylsilicones had lower moduli than analogous monophenylsilicones.     

Sweet like chocolate

A new crystalline form of αβ‐d ‐lactose prepared by oven drying a concentrated aqueous solution of d ‐lactose is a lesson in the power of observation and the rigorous analysis of powder samples.     

Ab initio structure and vibration-rotation dynamics of germylene,GeH2

Accurate structure and potential energy surface of germylene, GeH₂, in its ground electronic state ¹A₁ were determined from ab initio calculations using the coupled-cluster approach in conjunction with the correlation-consistent basis sets up to sextuple-zeta quality. The Born-Oppenheimer equilibrium structural parameters for the ¹A₁ state are estimated to be r_e(GeH) = 1.5793 Å and ∠_e(HGeH) = 91.19^∘. The term value T_e for the lowest excited electronic state ã³B₁ of GeH₂ is predicted to be 9140 cm^–1. The vibration-rotation energy levels for the ¹A₁ state of the ⁷⁴GeH₂, ⁷⁴GeD₂, ⁷²GeH₂, and ⁷⁰GeH₂ isotopologues were determined using a variational approach and compared with the experimental data. The role of the core-electron correlation, higher-order valence-electron correlation, scalar relativistic, spin-orbit, and adiabatic effects for prediction of the structure and vibration-rotation dynamics of the GeH₂ molecule is discussed. © 2019 Wiley Periodicals, Inc.     

Fe3O4 – Glutathione stabilized Ag nanoparticles: A new magnetically separable robust and facile catalyst for aqueous phase reduction of nitroarenes

The heterostructured Ag nanoparticles decorated Fe₃O₄ Glutathione (Fe₃O₄‐Glu‐Ag) nanoparticles (NPs) were synthesized by sonicating glutathione (Glu) with magnetite and further surface immobilization of silver NPs on it. The ensuing magnetic nano catalyst is well characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), powder X‐ray diffraction (PXRD), thermogravimetric analysis (TGA). The prepared Fe₃O₄‐Glu‐Ag nanoparticles have proved to be an efficient and recyclable nanocatalyst with low catalyst loading for the reduction of nitroarenes and heteronitroarenes to respective amines in the presence of NaBH₄ using water as a green solvent which could be easily separated at the end of a reaction using an external magnet and can be recycled up to 5 runs without any significant loss in catalytic activity. Gram scale study for the reduction of 4‐NP has also being carried out successfully and it has been observed that this method can serve as an efficient protocol for reduction of nitroarenes on industrial level.