Vanillin Formation by Electrooxidation of Lignin on Stainless Steel Anode: Kinetics and By-Products

Galvanostatic electrooxidation runs on stainless steel (SS-304) anode were carried out on soda lignins from wheat straw and bagasse obtained from acidification of respective soda black liquors. Vanillin concentration, produced during electrooxidation, is found to increase, attain a maximum, and then decline. Pseudo-first-order specific reaction rate constants for lignin degradation in electrooxidation over SS-304 anode were found to be 0.0308 and 0.0368 h^?1, respectively, for the two lignin samples. Degradation of vanillin during electrooxidation was found to be of second order with respect to vanillin concentration with specific reaction rate constant being 0.0009 L/(mg h). A kinetic model was proposed based on series-parallel multiple reaction scheme using a fourth-order Runge–Kutta iteration to fit the time-dependent vanillin concentration during electrooxidation. It was proposed that a vanillin precursor was formed from the parent lignin macromolecule with a pseudo-first-order specific reaction rate constant of 0.03 h^?1 for wheat straw soda lignin and 0.036 h^?1 for bagasse soda lignin. The vanillin precursor subsequently converted to vanillin with a pseudo-first-order specific reaction rate constant of 0.044 h^?1. In addition to vanillin, 4-hydroxy-3,5-dimethoxyphenyl ethanone, and 1,2-benzenedicarboxylic acid were detected as major by-products. Interestingly, some aliphatic and aromatic hydrocarbons were also formed.     

Integration of biofuels intermediates production and nutrients recycling in the processing of a marine algae

The cost‐effective production of liquid biofuels from microalgae is limited by several factors such as recovery of the lipid fractions as well as nutrients management. Flash hydrolysis, a rapid hydrothermal process, has been successfully applied to fractionate the microalgal biomass into solid biofuels intermediates while recovering a large amount of the nutrients in the aqueous phase (hydrolyzate) in a continuous flow reactor. The aim of the work is to enhance the quality of a high‐ash containing marine algae Nannochloropsis gaditana as biofuel feedstock while recycling nutrients directly for algae cultivation. Characterization of products demonstrated an increase in extractable lipids from 33.5 to 65.5 wt % (dry basis) while retaining the same fatty acid methyl ester profile, in addition to diminution of more than 70 wt % of ash compared to raw microalgae. Moreover, the hydrolyzate was directly used to grow a microalga of the same genus. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1494–1502, 2017     

Aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups: synthesis and characterization

A new bisphenol, 1,1-bis-[(4-hydroxyphenyl)-1-(4-phenylsulfonyl)phenyl)]ethane (DPSBP) was synthesized starting from diphenylsulfide and was characterized by spectroscopic methods. DPSBP was polycondensed with isophthalic acid chloride (IPC), terephthalic acid chloride (TPC) and a mixture of IPC and TPC (50:50 mol%) by phase-transfer catalysed interfacial polymerization method to obtain aromatic polyesters containing pendent 4-(phenylsulfonyl)phenyl groups. A series of copolyesters was also obtained by polycondensation of varying molar proportions of DPSBP and bisphenol-A (BPA) with TPC. (Co)polyesters exhibited inherent viscosities in the range 0.56–1.57 dLg^?1 and number average molecular weights (Mn) were in the range 28,650–80,230 g/mol. Polyesters dissolved readily in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran and aprotic polar solvents such as N-methylpyrrolidone, and N,N-dimethylacetamide. Tough, transparent and flexible films of polyesters could be cast from their chloroform solutions. X-Ray diffraction studies indicated amorphous nature of aromatic polyesters. Polyesters showed T_g values in the range 223–257 °C while T₁₀ values were in the range of 469–484 °C indicating their excellent thermal stability.     

Reactivity of Hydroxamate Ions in Cationic Vesicular Media for the Cleavage of Carboxylate Esters

The hydrolysis of carboxylate esters viz. p‐nitrophenyl acetate (PNPA), p‐nitrophenyl butyrate (PNPB) and p‐nitrophenyl octanoate (PNPO) in the presence of cationic vesicles of the surfactant dioctadecyldimethylammonium bromide (DODAC) by different hydroxamate ions i.e. acetohydroxamate (AHA^?), benzohydroxamate (BHA^?) and salicylhydroxamate (SHA^?) were studied. The kinetic data was supported by spectrophotometric measurements. The effects of vesicular size on the reaction have been discussed. The differential reactivity under endo‐ and exovesicular conditions has also been evaluated. Critical vesicle concentrations (CVC) of cationic vesicular surfactants were determined from conductometric and fluorimetric measurements at 300 K. Fluorescence probe pyrene and pyrene‐1‐carboxaldehyde have been used for determination of CVC. Further, thermodynamic parameters viz. Standard Gibb's energy (?G°), enthalpy (?H°), and entropy (?S°) of vesicles has also been evaluated within a temperature range of 303.15–328.15 K.     

Effect of iron oxide (Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>) on the structural,optical, electrical,and dielectric properties of SrO–V<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

The oxide glass system of the composition (10 – x)SrO–xFe₂O₃–90V₂O₅, (x = 0, 2, 4, 6 and 8 mol %) were prepared by a standard melt quenching technique. The amorphous nature of the prepared glass was confirmed using X-ray diffraction technique. The infrared spectra of these glasses were recorded over a continuous spectral range (850–1500 cm^–1). The density of prepared sample was obtained by the Archimedes principle. The physical parameters of the glasses were also determined with respect to the composition. Density increases from 3.10 to 3.20 g/cm³, whereas the molar volume decreases with the increase in Fe₂O₃ concentration. In order to study optical properties, absorption spectra were measured at room temperature. Indirect optical energy band gap, optical dielectric constant, refractive index were calculated from optical energy band gap. The refractive index decreases gradually with the increase in Fe₂O₃ content due to increase of bridging oxygen’s. For temperatures from 300 to 500 K, the dc conductivity increased with the increasing Fe₂O₃ content. The dielectric properties like dielectric constant, dielectric loss factor and dielectric loss tangent investigated at the room temperature in the frequency range of 10 kHz to 1 MHz decreases with frequency. The dielectric behavior shows strong frequency as well as composition dependence.     

Iterative Antimicrobial Candidate Selection from Informed D‐/L‐Peptide Dimer Libraries

Growing resistance to antibiotics, as well as newly emerging pathogens, stimulate the investigation of antimicrobial peptides (AMPs) as therapeutic agents. Here, we report a new library design concept based on a stochastic distribution of natural AMP amino acid sequences onto half‐length synthetic peptides. For these compounds, a non‐natural motif of alternating D ‐ and L ‐backbone stereochemistry of the peptide chain predisposed for β‐helix formation was explored. Synthetic D ‐/L ‐peptides with permuted half‐length sequences were delineated from a full‐length starter sequence and covalently recombined to create two‐dimensional compound arrays for antibacterial screening. Using the natural AMP magainin as a seed sequence, we identified and iteratively optimized hit compounds showing high antimicrobial activity against Gram‐positive and Gram‐negative bacteria with low hemolytic activity. Cryo‐electron microscopy characterized the membrane‐associated mechanism of action of the new D ‐/L ‐peptide antibiotics.     

Structural,vibrational, optical,magnetic and dielectric properties of Bi1−xBaxFeO3 nanoparticles

Bi_1−xBa_xFeO₃ (x=0.05, 0.10 and 0.15) nanoparticles were synthesized by the sol–gel method. X-ray diffraction and Raman spectroscopy results showed the presence of distorted rhombohedral structure of Bi_1−xBa_xFeO₃ nanoparticles. Rietveld refinement and Williamson–Hall plot of the x-ray diffraction patterns showed the increase in lattice parameters, unit cell volume and the particle size. Infrared spectroscopy and Raman analysis revealed the shifting of phonon modes towards the higher wavenumber side with increasing Ba concentration. These samples exhibited the optical band gap in the visible region (2.47–2.02 eV) indicating their ability to absorb visible light. Magnetic measurement showed room temperature ferromagnetic behavior, which may be attributed to the antiferromagnetic core and the ferromagnetic surface of the nanoparticles, together with the structural distortion caused by Ba substitution. The magnetoelectric coupling was evidenced by the observation of the dielectric anomaly in the dielectric constant and the dielectric loss near antiferromagnetic Neel temperature in all the samples.     

Effect of particle size on thermomechanical properties of particulate polymer composite

Particulate composite materials (PCM) consisting of a matrix reinforced by micro to nano-sized dispersed phase are receiving the attention of designers as a promising futuristic materials. This study unearths the thermal and mechanical behavior of maleic anhydride grafted polypropylene/silica (MA-g-PP/silica) composites for reinforcement ranging from micro- to nano-size. The monodisperse silica spherical particles were used in all the formulations of composites. Further the volume fraction was kept the same in all the compounded thermoplastic composites ranging from 100 nm to 130 μm in a co-rotating conical twin-screw micro-compounder. The micrographs were obtained from transmission electron microscopy (TEM) and the scanning electron microscopy (SEM). The SEM and TEM results revealed a good dispersion of the silica spheres within the MA-g-PP matrix. The compounded composite materials were injection molded to fabricate tensile test specimens (ASTM D638 type V) and tested for tensile properties. In order to investigate the effect of particle size on crystallite structure of the matrix, the composites were tested on differential scanning calorimeter and X-ray diffraction (WAXD). The thermal stability and degradation kinetics were studied via thermogravimetric analysis. The results show increase in crystallization rate, crystallinity percentage, Young’s modulus, strength and thermal stability of MA-g-PP by addition of the silica particles. Further it was observed that the small-sized dispersed phase had better overall thermal and mechanical behavior than its larger sized counterpart.     

Octane number enhancement studies of naphtha over noble metal loaded zeolite catalysts

An Indian industrial naphtha containing mixture of various hydrocarbons belong to n-paraffins, isoparaffins, naphthenes and aromatics falling in C₅ to C₉ carbon range has been studied for its octane boosting through the production of isoparaffins over various Pt loaded zeolite catalysts possessing different acidity and porosity properties. Optimum balance of acid and metal functionalities in 0.6 wt.% Pt loaded on BEA zeolite helped in achieving highest increase in research octane number (RON) from 44 to 80, suitable for gasoline applications, through the production of lower isoparaffins (iC₄-iC₆) along with C₇+ isoparaffins.     

Whale Optimization Algorithm Approach for Performance Optimization of Novel Xmas Tree-Shaped FinFET

Silicon - Today, Fin shaped Field Effect Transistors (FinFETs) are the framework of the sub-nanometer technology node. The leading semiconductor industry deploys it in low-power (LP) and...