Modeling the mechanism involved during the sorption of methylene blue onto fly ash

Batch sorption experiments were carried out to remove methylene blue from its aqueous solutions using fly ash as an adsorbent. Operating variables studied were initial dye concentration, fly ash mass, pH, and contact time. Maximum color removal was observed at a basic pH of 8. Equilibrium data were represented well by a Langmuir isotherm equation with a monolayer sorption capacity of 5.718 mg/g. Sorption data were fitted to both Lagergren first-order and pseudo-second-order kinetic models and the data were found to follow pseudo-second-order kinetics. Rate constants at different initial concentrations were estimated. The process mechanism was found to be complex, consisting of both surface adsorption and pore diffusion. The effective diffusion parameter D(i) values were estimated at different initial concentrations and the average value was determined to be 2.063 x 10(-9)cm2/s. Analysis of sorption data using a Boyd plot confirms the particle diffusion as the rate-limiting step for the dye concentration ranges studied in the present investigation (20 to 60 mg/L).     

Autocatalytic O2 cleavage by an OCO3 trianionic pincer Cr(III) complex: isolation and characterization of the autocatalytic intermediate [Cr(IV)]2(μ-O) dimer

Synthetic and kinetic experiments designed to probe the mechanism of O(2) activation by the trianionic pincer chromium(III) complex [(t)BuOCO]Cr(III)(THF)(3) (1) (where (t)BuOCO = [2,6-((t)BuC(6)H(3)O)(2)C(6)H(3)](3-), THF = tetrahydrofuran) are described. Whereas analogous porphyrin and corrole oxidation catalysts can become inactive toward O(2) activation upon dimerization (forming a μ-oxo species) or product inhibition, complex 1 becomes more active toward O(2) activation when dimerized. The product from O(2) activation, [(t)BuOCO]Cr(V)(O)(THF) (2), catalyzes the oxidation of 1 via formation of the μ-O dimer {[(t)BuOCO]Cr(IV)(THF)}(2)(μ-O) (3). Complex 3 exists in equilibrium with 1 and 2 and thus could not be isolated in pure form. However, single crystals of 3 and 1 co-deposit, and the molecular stucture of 3 was determined using single-crystal X-ray crystallography methods. Variable (9.5, 35, and 240 GHz) frequency electron paramagnetic resonance spectroscopy supports the assignment of complex 3 as a Cr(IV)-O-Cr(IV) dimer, with a high (S = 2) spin ground state, based on detailed computer simulations. Complex 3 is the first conclusively assigned example of a complex containing a Cr(IV) dimer; its spin Hamiltonian parameters are g(iso) = 1.976, D = 2400 G, and E = 750 G. The reaction of 1 with O(2) was monitored by UV-visible spectrophotometry, and the kinetic orders of the reagents were determined. The reaction does not exhibit first-order behavior with respect to the concentrations of complex 1 and O(2). Altering the THF concentration reveals an inverse order behavior in THF. A proposed autocatalytic mechanism, with 3 as the key intermediate, was employed in numerical simulations of concentration versus time decay plots, and the individual rate constants were calculated. The simulations agree well with the experimental observations. The acceleration is not unique to 2; for example, the presence of OPPh(3) accelerates O(2) activation by forming the five-coordinate complex trans-[(t)BuOCO]Cr(III)(OPPh(3))(2) (4).     

Influence of supporting electrolytes on the structure of electrodeposited SnO<Subscript>2</Subscript> thin films for energy storage applications

Different SnO₂ nanostructures (SnO₂Ns) were directly electrodeposited on the surface of anodized copper (Cu) substrates via the potentiostatic electrodeposition method with addition of supporting electrolytes. The effects of the supporting electrolytes and the electrodeposition parameters on the evolution of nanostructures and on the electrochemical properties of the SnO₂Ns were systematically investigated using field emission scanning electron microscope (FESEM) and electrochemical methods including cyclic voltammetry (CV) and chronoamperometry (CA). The results confirmed that SnO₂Ns exhibit alloying/de-alloying reactions with Li⁺ ions versus Ag/AgCl in aqueous electrolyte solution (LiOH·H₂O and Li₂CO₃). The super capacitor performance of the SnO₂Ns was investigated in 0.5-M Na₂SO₄ aqueous solution, and the highest specific capacitance of 110 Fg^?1 at a scan rate of 5 mV s^?1 was obtained for SnO₂ microspheres made up of nanocubes. Our study shows that supporting electrolytes and electrodeposition parameters play the significant role in the growth of SnO₂Ns and its electrochemical properties.     

Advanced electrocatalytic materials based biosensors for cancer cell detection – A review

Herein, we have highlighted the latest developments on biosensors for cancer cell detection. Electrochemical (EC) biosensors offer several advantages such as high sensitivity, selectivity, rapid analysis, portability, low-cost, etc. Generally, biosensors could be classified into other basic categories such as immunosensors, aptasensors, cytosensors, electrochemiluminescence (ECL), and photo-electrochemical (PEC) sensors. The significance of the EC biosensors is that they could detect several biomolecules in human body including cholesterol, glucose, lactate, uric acid, DNA, blood ketones, hemoglobin, and others. Recently, various EC biosensors have been developed by using electrocatalytic materials such as silver sulfide (Ag₂S), black phosphene (BPene), hexagonal carbon nitrogen tube (HCNT), carbon dots (CDs)/cobalt oxy-hydroxide (CoOOH), cuprous oxide (Cu₂O), polymer dots (PDs), manganese oxide (MnO₂), graphene derivatives, and gold nanoparticles (Au-NPs). In some cases, these newly developed biosensors could be able to detect cancer cells with a limit of detection (LOD) of 1 cell/mL. In addition, many remaining challenges have to be addressed and validated by testing more real samples and confirm that these EC biosensors are more accurate and reliable to measure cancer cells in the blood and salivary samples.     

High-accuracy large-step explicit Runge–Kutta (HALE-RK) schemes for computational aeroacoustics

In many realistic calculations, the computational grid spacing required to resolve the mean flow gradients is much smaller than the grid spacing required to resolve the unsteady propagating waves of interest. Because of this, the high temporal resolution provided by existing optimized time marching schemes can be excessive due to the small time step required for stability in regions of clustered grid. In this work, explicit fourth-order accurate Runge–Kutta time marching schemes are optimized to increase the inviscid stability limit rather than the accuracy at large time steps. Single and multiple-step optimized schemes are developed and analyzed. The resulting schemes are validated on several realistic benchmark problems.     

Structure and function of propranolol: A β-adrenergic blocking drug

In our earlier studies using quantum chemical methods we had proposed that propranolol has an extended structure. These results were confirmed using proton NMR . We have now carried out extensive magnetic resonance and model building studies to examine the interaction of this drug with model membranes. The effect of propranolol on organization of lipid bilayers has been studied using ESR spin labeling technique. Spin label Tempo and spin labeled stearic acid (5 SASL ) have been used to monitor changes in the fluidity of model membranes. Presence of the drug is found to fluidize the lipids. In case of 0.2M dipalmitoyl phosphatidyl choline (DPPC), presence of drug (0.1M) is found to decrease the gel-liquid crystalline phase transition temperature by about 10°C. The order parameter measured from the spectrum of 5 SASL shows a 4% decrease on incorporation of the drug in membranes. ¹³C spin lattice relaxation time (T₁) measurements have been carried out for different nuclear sites of the drug. The aromatic moiety shows a high degree of molecular rigidity when the drug is bound to the lipid bilayers. The oxypropanolamine group is however relatively flexible. It appears from these studies that the aromatic group binds strongly to the hydrophobic regions of the lipid bilayer, while the oxypropanolamine moiety remains relatively free and lies in the hydrophilic region. The ¹³C chemical shifts indicate the involvement of the β-hydroxyl group in hydrogen bonding with the lipids. The NH group may be involved in electrostatic interactions with the negatively charged phosphate group of the lipid bilayers.