Synthesis, characterization and coordination properties of bis(alkyl)selenosalen ligands

New bis (alkyl) selenosalen podand ligands having Se2N2 donor sites have been synthesized by the condensation of unsymmetrical o-formylphenyl alkyl selenide (1-3) with ethylenediamine. The reaction of bis(alkyl)selenosalen podands with Pd(II) and Pt(II) afforded selenoether-selenolate coordination complexes 7-10via cleavage of one of the two Se-C(alkyl) bonds of bis(alkyl)selenosalen podands upon complexation. DFT calculations revealed that the cleavage of Se-C(alkyl) bonds occurred possibly via S(N)2 mechanism instead of a sequence of oxidative addition and reductive elimination reactions. The spectral data and elemental analyses confirmed the formation of selenoether-selenolate complexes. The structures of the podands N,N'-bis[(2-methylseleno)phenylmethylene]-1,2-ethanediamine (4), N,N'-bis[(2-decylseleno)phenylmethylene]-1,2-ethanediamine (5) and the selenoether-selenolate complex 8 have been determined by single crystal X-ray diffraction analysis. The crystal structure of 5 showed SeH interaction with a ladder like 3D supramolecular arrangement via interdigitation of long alkyl chains. Comparison of crystal packing of podands 4 and 5 indicates that the alkyl chain length has significant impact on the crystal packing. The platinum selenolate complex 8 shows a square planar arrangement around the Pt centre, where the Se atoms in the selenolate and the selenoether have nearly equal Pt-Se bond length.     

Utility of calculated 13C NMR chemical shifts in differentiating conformational isomers: a study of metal-complexed and uncomplexed bispidines

Calculated 13C NMR chemical shifts were key to assigning the structures of the conformational forms of complexed and uncomplexed bispidine derivatives.     

Quark matter nucleation in hot hadronic matter

We study the quark deconfinement phase transition in hot β-stable hadronic matter. Assuming a first order phase transition, we calculate the enthalpy per baryon of the hadron–quark phase transition. We calculate and compare the nucleation rate and the nucleation time due to thermal and quantum nucleation mechanisms. We compute the crossover temperature above which thermal nucleation dominates the finite temperature quantum nucleation mechanism. We next discuss the consequences for the physics of proto-neutron stars. We introduce the concept of limiting conversion temperature and critical mass M_cr for proto-hadronic stars, and we show that proto-hadronic stars with a mass M<M_cr could survive the early stages of their evolution without decaying to a quark star.     

An HPTLC Method for the Simultaneous Analysis of Compactin and Citrinin in Penicillium citrinum Fermentation Broth

JPC – Journal of Planar Chromatography – Modern TLC - A simple and precise high-performance thin-layer chromatographic (HPTLC) method has been established for simultaneous analysis of...     

Phase transformation and optical properties of Cu-doped ZnS nanorods

ZnS nanorods doped with 0-15 mol% of Cu have been prepared by simple solvothermal process. With gradual increase in the Cu concentration, phase transformation of the doped ZnS nanorods from wurtzite to cubic was observed. Twins and stacking faults were developed due to atomic rearrangement in the heavily doped ZnS nanorods during phase transformation. UV-vis-NIR absorbance spectroscopy ruled out the presence of any impure Cu-S phase. The doped ZnS nanorods showed luminescence over a wide range from UV to near IR with peaks at 370, 492-498, 565 and 730 nm. The UV region peak is due to the near-band-edge transition, whereas, the green peak can be related to emission from elementary sulfur species on the surfaces of the nanorods. The orange emission at 565 nm may be linked to the recombination of electrons at deep defect levels and the Cu(t₂) states present near the valence band of ZnS. The near IR emission possibly originated from transitions due to deep-level defects.     

Convex fuzzy mapping with differentiability and its application in fuzzy optimization

The concepts of differentiability, convexity, generalized convexity and minimization of a fuzzy mapping are known in the literature. The purpose of this present paper is to extend and generalize these concepts to fuzzy mappings of several variables using Buckley–Feuring approach for fuzzy differentiation and derive Karush–Kuhn–Tucker condition for the constrained fuzzy minimization problem.     

Time-average measurement of velocity, density, temperature, and turbulence velocity fluctuations using Rayleigh and Mie scattering

Measurement of time-averaged velocity, density, temperature, and turbulence velocity fluctuations in sparsely seeded gas flows using a non-intrusive, point-wise technique based on Rayleigh and Mie scattering is discussed. A Fabry-Perot interferometer (FPI) is used to spectrally resolve laser light scattered by molecules and particulates in gas flows. The spectral content of the scattered light provides information about velocity, density, and temperature of the gas. A CCD camera is used to record images of the fringes formed by scattered light passing through the interferometer. Models of the spectral components are used in a least squares fitting routine to estimate the parameters from fringe images. Flow measurements are presented for subsonic and supersonic jet flows. The application range for this technique is mostly for high velocity situations (>25 m/s). Velocity, density, temperature, and turbulence velocity fluctuations were determined with accuracies within 5 m/s, 4%, 2%, and 5 m/s, respectively.     

Expedient Access to Enantioenriched 1-Azaspiro Cyclobutanones Enabled by Modified Heyns Rearrangement

Leveraging the unexplored regions of chemical space, the integration of spirocyclic cyclobutane in a molecular scaffold opens up a new vista in modern drug discovery. Despite recent advancements in achieving the synthesis of such motifs, strategies for their asymmetric construction have not been well-recognized and remain a formidable challenge. Herein, for the first time, we have demonstrated a chiral Brønsted acid-catalyzed enantioselective synthesis of 1-azaspiro cyclobutanone enabled by an unusual reactivity of enamine that explore the potentiality of Heyns rearrangement upon electrophilic modification. This design strategy offers viable access to a wide range of cyclobutanone containing spiroindoline and spiropyrrolidine derivatives in good yields with excellent stereoselectivities (up to >99 % ee, >20 : 1 dr). Furthermore, the practicality of this methodology has been shown by a scale-up synthesis of spirocyclic products and their facile post-synthetic modifications.     

Polymeric Nanoformulation of Zoledronic Acid Rescues Osteoblasts from the Harmful Effect of its Native Form: An In Vitro Investigation of Cytotoxic Potential on Osteoblasts and Osteosarcoma Cells

Osteosarcoma (OS) is a malignant tumor, fatal for pediatric patients who do not respond to chemotherapy, alternative therapies and drugs can provide better outcomes. Zoledronic acid (Zol) belonging to the class of bisphosphonates (BPs) has a direct antitumor ability to prevent Ras GTPases modification and stimulate apoptosis. Despite advances in maintaining balance in skeletal events and direct anticancer properties, Zol causes cytotoxicity to normal healthy pre-osteoblast cells, hampering mineralization and differentiation. The study reports the preparation and evaluation of a nanoformulation that can diminish the existing drawbacks of native Zol. The cytotoxic effect is evaluated on bone cancer cells and healthy bone cells with three different cell lines namely, K7M2 (mouse OS cell line), SaOS2 (human OS cell line), and MC3T3E1 (healthy cell counterpart). It is observed that Zol nanoformulation is uptaken more (95%) in K7M2 whereas in MC3T3E1, the percent population internalizing nanoparticles (NPs) is 45%. Zol has a sustained release of 15% after 96 h from the NP which leads to a rescuing effect on the normal pre-osteoblast cells. In conclusion, it can be stated that Zol nanoformulation can be used as a good platform for a sustained release system with minimum side effects to normal bone cells.     

Transition-Metal-Free Heterocyclic Carbon-Boron Bond Formation

Heteroaryl boronic acids and esters are extremely important and valuable intermediates because of their wide application in the synthesis of marketed drugs and bioactive compounds. Over the last couple of decades, the construction of highly important heteroaryl carbon-boron bonds has created huge attention. The transition-metal-free protocols are more green, less sensitive to air and moisture, and also economically advantageous over the transition-metal-based protocols. The transition-metal-free C−H borylation of heteroarenes and C−X (X=halogen) borylation of heteroaryl halides represents an excellent approach for their synthesis. Also, various cyclization and alkyne activation protocols have been recently established for their synthesis. The goal of this review article is to summarize the existing literature and the current state of the art for transition-metal-free synthesis of heteroaryl boronic acid and esters.