Spectroscopic study of solid benzene and benzene isolated in rare-gas matrices

Absorption and luminescence excitation spectra of solid benzene and benzene isolated in rare-gas matrices have been studied. The absolute absorption cross sections of various electronic band systems including the Rydberg region of C₆H₆ are obtained using transmission spectra of C₆H₆-doped rare-gas films of different thickness. An interpretation of the structure in the Rydberg region is given in terms of two Rydberg series using the quantum defect method. A comparative study has been made of luminescence excitation spectra of matrix-isolated and of pure C₆H₆. The luminescence excitation spectra of matrix-isolated benzene gives information on the internal conversion and medium-induced vibrational relaxation.     

Isolation and characterization of crotosparsamide, a new cyclic nonapeptide from Croton sparsiflorus

Crotosparsamide (1), a new cyclic nonapeptide, has been isolated from the n-butanol soluble sub-fraction of Croton sparsiflorus along with p-hydroxy methylcinnamate and kaempferol, which are reported for the first time from this species. Their structures were determined by chemical and spectral studies including ESIMS, and 1D and 2D NMR spectroscopic data.     

Biodiesel Production from Alkali-Catalyzed Transesterification of Tamarindus indica Seed Oil and Optimization of Process Conditions

Biodiesel is considered a sustainable alternative to petro-diesel owing to several favorable characteristics. However, higher production costs, primarily due to the use of costly edible oils as raw materials, are a chief impediment to its pecuniary feasibility. Exploring non-edible oils as raw material for biodiesel is an attractive strategy that would address the economic constraints associated with biodiesel production. This research aims to optimize the reaction conditions for the production of biodiesel through an alkali-catalyzed transesterification of Tamarindus indica seed oil. The Taguchi method was applied to optimize performance parameters such as alcohol-to-oil molar ratio, catalyst amount, and reaction time. The fatty acid content of both oil and biodiesel was determined using gas chromatography. The optimized conditions of alcohol-to-oil molar ratio (6:1), catalyst (1.5% w/w), and reaction time 1 h afforded biodiesel with 93.5% yield. The most considerable contribution came from the molar ratio of alcohol to oil (75.9%) followed by the amount of catalyst (20.7%). In another case, alcohol to oil molar ratio (9:1), catalyst (1.5% w/w) and reaction time 1.5 h afforded biodiesel 82.5% yield. The fuel properties of Tamarindus indica methyl esters produced under ideal conditions were within ASTM D6751 biodiesel specified limits. Findings of the study indicate that Tamarindus indica may be chosen as a prospective and viable option for large-scale production of biodiesel, making it a substitute for petro-diesel.     

Photoluminescence emission behavior on the reduced band gap of Fe doping in CeO2-SiO2 nanocomposite and photophysical properties

Fe/CeO₂-SiO₂ nanocomposite was synthesized via hydrothermal method. Bond length of nanocomposite was determined through FTIR analysis, while Raman analysis showed lattice relaxation of CeO₂ phase in Fe/CeO₂-SiO₂. TEM, XRD and DLS-PSA revealed an increase in size of Fe/CeO₂-SiO₂ as compared to CeO₂-SiO₂ which was attributed to have more oxygen vacancies in CeO₂ after doping of iron. Lattice contraction was also observed in some phases of CeO₂ in Fe/CeO₂-SiO₂ nanocomposite as compared to CeO₂-SiO₂ nanocomposite. This contraction was used for determination of Fe content incorporated in CeO₂ [1 1 1] phase. The band gap values of Fe/CeO₂-SiO₂ nanocomposite were found reduced after doping of Fe by factors of 0.62 and 0.55 eV, respectively. Photoluminescence study of the materials was carried out to study the different type of transitions occurring after absorption of electromagnetic radiation. Photoluminescence intensity at 2.12 eV was found enhanced after doping of Fe due to increased oxygen vacancy. Photocatalytic activity of the nanocomposites was studied with the degradation of chlorpyrifos pesticide.     

Transverse Transport of Polymeric Nanofluid under Pure Internal Heating: Keller Box Algorithm

The present work aims to investigate transverse Oldroyd-B nanofluid flow on a stretched panel with consideration of internal heat generation. Buongiorno model is utilized to study influence of thermophoresis and Brownian motion effects. A numerical procedure known as Keller box algorithm is used to solve the governed physical model.Graphically velocity, temperature and concentration of nanoparticles are expressed. Also, concerned physical measures such as heat and mass transfer are investigated numerically. The simulations performed revealed that fluid parameters play a significant role in heat transfer under Brownian motion and thermophoresis effects. Local heat flux is elevated while local mass flux is suppressed with enhancing Brownian motion parameter. Streamlines pattern exhibits that flow is more inclined in the presence of Deborah number effects. To the best of our knowledge, transverse flow of an Oldroyd-B type fluid which incorporates the thermal relaxation effects has never been reported before in the presence of Brownian motion and internal heating phenomenon. Therefore we intend to discuss these features in detail. The obtained results are a novel contribution, which can be benchmark for further relevant academic research related to polymer industry.     

First-principle electronic, elastic, and optical study of cubic gallium nitride

The ab initio pseudopotential (PP) method within the generalized gradient approximation (GGA) has been used to investigate the electronic, elastic constants, and optical properties of zinc-blende GaN. An underestimated band gap along with higher DOS and squeezed energy bands around the fermi level is obtained. The d-band effect is briefly discussed for electronic band structure calculations. With the help of elastic constants, acoustic wave speeds are calculated in [100], [110], and [111] planes. The dielectric constant, refractive index, and its pressure coefficient are well illustrated. The effect of hydrostatic pressure is explicated for all these properties. The results of the present study are evaluated with the existing experimental and first-principle calculations.     

Eremosides A – C,New Iridoid Glucosides from Eremostachys loasifolia

Eremosides A–C ( 1 – 3 ), three new iridoid glucosides, were isolated from the AcOEt‐soluble fraction of the EtOH extract of the whole plant of Eremostachys loasifolia, along with buddlejoside B ( 4 ), 10‐O‐benzoylcatalpol ( 5 ), and pakiside A ( 6 ) reported for the first time from this species. The structures of these compounds were elucidated by spectroscopic data including 2D‐NMR, FAB‐MS, ESI‐MS, as well as by acid and basic hydrolyses.     

EPR Study of γ-Irradiated UHMWPE Doped with Vitamin E: Assessment of Thermal Effects on the Organic Radicals During Vitamin E Diffusion

Thermal effects on ultra-high-molecular-weight polyethylene (UHMWPE) residual radicals during the vitamin E diffusion process were studied in detail. Electron paramagnetic resonance (EPR) technique showed a significant reduction in concentrations of radiation-induced primary (alkyl (–CH₂– ^?CH–CH₂–), allyl (–CH₂–^?CH=CH–CH–CH₂–) and polyenyl (–^?CH–[CH=CH–] _m –) with m > 3) radicals for both control and vitamin E-doped samples. The concentrations of radiation-induced primary radicals (RIPRs) were found to decrease proportionally with the heat/diffusion time. While the EPR spectra of the control samples showed only polyethylene (PE) radicals, the spectra of vitamin E-doped samples were found to exhibit vitamin E radicals in addition to PE radicals. Of particular interest, the heat involved during vitamin E diffusion plays a significant role in reducing the radiation-induced primary radicals of UHMWPE. For 120 min of heat/diffusion time, the available quantity of primary radicals in control samples were found to be ~7.5 % of initial radicals. The leftover amounts of these primary radicals for vitamin E-doped samples were approximately ~10.0 %. In addition to this, EPR power saturation techniques were also used to assess the effects of initial heat/diffusion treatment on the oxygen-induced residual radicals (OIRRs): R₁ (–^?CH–[CH=CH–] _m –) with m > 3 and R₂ (^?OCH–[CH=CH–] _m –) with m = 2 or 3. It was found that the concentration of OIRRs also decreases proportionally with initial heat/diffusion time. The remaining amount of OIRRs relative to leftover RIPRs after heat/diffusion was found to be approximately 4.0 % in controls and was still found to be 10.0 % in vitamin E-doped UHMWPE. This may indicate that vitamin E slows down the oxidation processes, which may contribute to the strong oxidation resistance of vitamin E-doped UHMWPE.     

A distal pocket Leu residue inhibits the binding of O2 and NO at the distal heme site of cytochrome c'

Cytochromes c' are pentacoordinate heme proteins with sterically hindered distal sites that bind NO and CO but do not form stable complexes with O(2). Removal of distal pocket steric hindrance via a Leu→Ala mutation yields favorable O(2) binding (K(d) ~49 nM) without apparent H-bond stabilization of the Fe-O(2) moiety, as well as an extremely high distal heme-NO affinity (K(d) ~70 fM). The native Leu residue inhibits distal coordination of diatomic ligands by decreasing k(on) as well as increasing k(off). The connection between distal steric constraints, k(off) values, and distal to proximal heme-NO conversion is discussed.