A new class of spherically symmetric gravitational collapse

Theoretical and Mathematical Physics - We discuss the gravitational collapse of a spherically symmetric perfect fluid distribution of uniformly contracting stars. In a uniformly contracting star,...     

Influence of the addition of aluminium nanoparticles on thermo-rheological properties of hydroxyl-terminated polybutadiene-based composite propellant and empirical modelling

The heat transfer performance and entropy analysis are done in a compact loop heat pipe (CLHP) with Al₂O₃/water and Ag/water nanofluid. A compact loop heat pipe having a flat square evaporator with dimensions of 34 mm (L)?×?34 mm (W)?×?19 mm (H) has been fabricated and tested for the heat load ranging from 30 to 500 W. The experimental tests are conducted by keeping the CLHP in the vertical orientation with distilled water, silver (Ag)/water and aluminium oxide (Al₂O₃)/water nanofluid having low volume concentrations of (0.09% and 0.12%). The effect of wall and vapour temperature, evaporator and condenser heat transfer coefficient, thermal resistance on the applied heat loads is experimentally investigated and compared. The experimental results showed that the evaporator thermal resistance is reduced by 34.70% and 20.21%, respectively, for 0.12 vol% of Ag, Al₂O₃ nanoparticles when compared with that of the distilled water. For the same volume concentrations of Ag, Al₂O₃ nanoparticles, an enhancement of 34.52%, 23.7%, 39.27% and 30.8%, respectively, observed for the convective heat transfer coefficients at the evaporator and condenser. The entropy is also reduced by 19.08% and 11.58% when Ag and Al₂O₃ nanofluids are used as the operating fluid. From the experimental tests, it is found that the addition of small amount of Ag nanoparticles in the working fluid enhanced the operating range by 15% when compared with that of Al₂O₃/water nanofluid without the occurrence of any dry-out conditions.

     

Influence of pyridine oximate and quaternized pyridinium oximate ions on the hydrolysis of phosphate esters in cationic microemulsions

Kinetic studies have been performed to understand the hydrolytic potencies of oximate (2- and 4-pyridinealdoxime) and its functionalized oximate (4-(hydroxyiminomethyl)-1-alkylpyridinium bromide) ions (alkyl?=?C₁₀H₂₁ (4-C₁₀PyOx^-); alkyl?=?C₁₂H₂₅ (4-C₁₂PyOx^-)) in the cleavage of phosphate esters, diethyl p-nitrophenylphosphate (Paraoxon) and p-nitrophenyl diphenyl phosphate (PNPDPP) in a cationic (O/W) microemulsion system (ME) over a pH range 7.5 to 11.0 at 300?K. The k_obs values for the reaction of paraoxon with oximate and its functionalized oximate were determined in different microemulsion composition and the kinetic rate data shows that k_obs values increases with increasing water content. The specificity of different chain length of alcohols (n-butanol, n-pentanol, n-hexanol and n-octanol) was also investigated in hydrolytic reactions of paraoxon for different microemulsion composition.     

Mathematical model of micropolar fluid in two-phase immiscible fluid flow through porous channel

This paper is concerned with the flow of two immiscible fluids through a porous horizontal channel. The fluid in the upper region is the micropolar fluid/the Eringen fluid, and the fluid in the lower region is the Newtonian viscous fluid. The flow is driven by a constant pressure gradient. The presence of micropolar fluids introduces additional rotational parameters. Also, the porous material considered in both regions has two different permeabilities. A direct method is used to obtain the analytical solution of the concerned problem. In the present problem, the effects of the couple stress, the micropolarity parameter, the viscosity ratio, and the permeability on the velocity profile and the microrotational velocity are discussed. It is found that all the physical parameters play an important role in controlling the translational velocity profile and the microrotational velocity. In addition, numerical values of the different flow parameters are computed. The effects of the different flow parameters on the flow rate and the wall shear stress are also discussed graphically.     

A metabolically engineered spin-labeling approach for studying glycans on cells

Metabolic glycan engineering (MGE) coupled with nitroxide spin-labeling (SL) was utilized to investigate the heterogeneous environment of cell surface glycans in select cancer and normal cells. This approach exploited the incorporation of azides into cell surface glycans followed by a click reaction with a new nitroxide spin label. Both sialic acid and N-acetylglucosamine (GlcNAc) were targeted for spin labelling. Although each of these moieties experiences a diverse and heterogeneous glycan environment, their EPR spectra and hence mobility are both characterized as a linear combination of two distinct spectra where one component reflects a highly mobile or uncrowded micro-environment with the second component reflecting more restricted motion, reflective of increased crowding and packing within the glycocalyx. What differs among the spectra of the targeted glycans is the relative percentage of each component, with sialic acid moieties experiencing on average an ∼80% less crowded environment, where conversely GlcNAc/GalNAz labeled sites reported on average a ∼50% more crowded environment. These distinct environments are consistent with the organization of sugar moieties within cellular glycans where some residues occur close to the cell membrane/protein backbone (i.e. more restricted) and others are more terminal in the glycan (i.e. more mobile). Strikingly, different cell lines displayed varied relative populations of these two components, suggesting distinctive glycan packing, organization, and composition of different cells. This work demonstrates the capability of SDSL EPR to be a broadly useful tool for studying glycans on cells, and interpretation of the results provides insights for distinguishing the differences and changes in the local organization and heterogeneity of the cellular glycocalyx.

Metabolic glycan engineering (MGE) coupled with nitroxide spin-labeling (SL) was utilized to investigate the heterogeneous environment of cell surface glycans in select cancer and normal cells.     

Fine‐Tuning of Lewis Acidity: The Case of Borenium Hydride Complexes Derived from Bis(phosphinimino)amide Boron Precursors

Reactions of bis(phosphinimino)amines LH and L′H with Me₂S ? BH₂Cl afforded chloroborane complexes LBHCl ( 1 ) and L′BHCl ( 2 ), and the reaction of L′H with BH₃ ? Me₂S gave a dihydridoborane complex L′BH₂ ( 3 ) (LH=[{(2,4,6‐Me₃C₆H₂N)P(Ph₂)}₂N]H and L′H=[{(2,6‐iPr₂C₆H₃N)P(Ph₂)}₂N]H). Furthermore, abstraction of a hydride ion from L′BH₂ ( 3 ) and LBH₂ ( 4 ) mediated by Lewis acid B(C₆F₅)₃ or the weakly coordinating ion pair [Ph₃C][B(C₆F₅)₄] smoothly yielded a series of borenium hydride cations: [L′BH]⁺[HB(C₆F₅)₃]^? ( 5 ), [L′BH]⁺[B(C₆F₅)₄]^? ( 6 ), [LBH]⁺[HB(C₆F₅)₃]^? ( 7 ), and [LBH]⁺[B(C₆F₅)₄]^? ( 8 ). Synthesis of a chloroborenium species [LBCl]⁺[BCl₄]^? ( 9 ) without involvement of a weakly coordinating anion was also demonstrated from a reaction of LBH₂ ( 4 ) with three equivalents of BCl₃. It is clear from this study that the sterically bulky strong donor bis(phosphinimino)amide ligand plays a crucial role in facilitating the synthesis and stabilization of these three‐coordinated cationic species of boron. Therefore, the present synthetic approach is not dependent on the requirement of weakly coordinating anions; even simple BCl₄^? can act as a counteranion with borenium cations. The high Lewis acidity of the boron atom in complex 8 enables the formation of an adduct with 4‐dimethylaminopyridine (DMAP), [LBH ? (DMAP)]⁺[B(C₆F₅)₄]^? ( 10 ). The solid‐state structures of complexes 1 , 5 , and 9 were investigated by means of single‐crystal X‐ray structural analysis.     

Hydrolytic Cleavage of Paraoxon by Octanohydroxamate Ion in Cationic Microemulsions

The hydrolysis reaction of O,O‐diethyl O‐p‐nitrophenylphosphate (Paraoxon) with the octanohydroxamate ion (OHA^?) was studied in a cationic oil‐in‐water (O/W) microemulsion system over a pH range 7.5–12.0 at 300 K. The O/W systems are stabilized by using cationic surfactant, cetyltrimethylammonium bromide (CTAB), and n‐butanol as cosurfactants. In a microemulsion, the rate enhancement by OHA^? is greater toward the cleavage of paraoxon than its spontaneous (2.1 × 10⁷ s^?1) hydrolysis. The k_obs values for the reaction of paraoxon with OHA^? were determined in different microemulsion compositions with varying chain length of alcohols (n‐butanol, n‐pentanol, n‐octanol, and n‐dodecanol) and alkanes (n‐hexane, n‐heptane, and n‐decane). The effects of water content, pH, and size of the oil pool have been discussed.     

Rapid and cost-effective LC–MS/MS method for determination of hydroxycitric acid in plasma: Application in the determination of pharmacokinetics in commercial Garcinia preparations

Garcinia cambogia is one of the most commonly used anti-obesity dietary supplements, and hydroxycitric acid (HCA) is a major constituent in the commercial preparations of Garcinia. High doses of HCA are often consumed without much awareness of its pharmacokinetic and toxicokinetic parameters, and therefore, a complete understanding of its effects is lacking. The first step in understanding these parameters is the availability of a reliable bioanalytical method. Here, we present the first report on a UPLC–MS/MS method for analysis of HCA in rat plasma after a simplified and cost-effective protein precipitation. Chromatographic separation of the analytes in the supernatant was achieved using hydrophilic interaction liquid chromatography, where mass parameters were optimized and a rapid 5-min quantitative assay was developed. The method was highly sensitive, accurate, precise and linear in the concentration range of 10.5–5000 ng/mL (validated according to the United States Food and Drug Administration guidelines). Further, the method was successfully used to describe the pharmacokinetic profile of HCA in rat plasma after the administration of pure HCA and commercial Garcinia preparations.     

Cu (II) and Co (II/III) complexes of N,O‐chelated Schiff base ligands: DNA interaction,protein binding,cytotoxicity, cell death mechanism and reactive oxygen species generation studies

A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH ₂ (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH ₂ = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC₅₀ values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished.