Regeneration of levulinic acid from loaded-organic phase: equilibrium,kinetic studies and process economics

Regeneration of carboxylic acids from the loaded-organic phase is an essential step to complete the reactive extraction process. A study on the regeneration of levulinic acid from loaded-organic phase (methyl isobutyl ketone + tri-n-octylamine + acid) was carried out using various techniques including NaOH, temperature swing, diluent swing, and tri-methylamine methods. Equilibrium data obtained show that among all the methods, the recovery of acid is the highest for the tri-methylamine method when the molar ratio of tri-methylamine to levulinic acid concentrations is greater than 1. Kinetic studies performed for the tri-methylamine method showed that there are no changes in the specific rate of extraction with changes in stirrer speed rate and phase volume ratio (V _aq/V _org), and the overall order of reaction is 1.5. Based on the effects of stirrer speed and phase volume ratio on the specific rate of extraction, the reaction was concluded to occur in the fast regime. Also, about 80% of acid was recovered by the evaporation of tri-methylamine phase at 104–140 °C. A detailed economic evaluation for the recovery of levulinic acid using reactive extraction for a feed rate of 2 m³ h^?1 shows that the payback period for recovering capital investment is 0.49 years.     

Synthesis of 1,2-naphthalenediol derivatives by Rh-catalyzed intermolecular OH insertion reaction of 1,2-diazonaphthoquinones with water and alcohols

Rh(II)-catalyzed OH insertion reaction of diazonaphthoquinones with water or alocohols proceeded to yield 1,2-naphthalenediol derivatives.     

Spectroscopy of η′ Mesic Nuclei with (p, d) Reaction

We are going to perform an inclusive spectroscopy experiment of η′ mesic nuclei with the ¹²C(p,d) reaction to study in-medium properties of the η′ meson. In nuclear medium, the η′ meson mass may be reduced due to partial restoration of chiral symmetry. In case of sufficiently large mass reduction and small absorption width of η′ at normal nuclear density, peak structures of η′ mesic states in ¹¹C will be observed near the η′ emission threshold even in an inclusive spectrum. The experiment will be carried out at GSI with proton beam supplied by SIS using FRS as a spectrometer. The detail of the experiment is described.     

Brillouin zone unfolding of complex bands in a nearest neighbour tight binding scheme

Complex bands k(⊥)(E) in a semiconductor crystal, along a general direction n, can be computed by casting Schr?dinger's equation as a generalized polynomial eigenvalue problem. When working with primitive lattice vectors, the order of this eigenvalue problem can grow large for arbitrary n. It is, however, possible to always choose a set of non-primitive lattice vectors such that the eigenvalue problem is restricted to be quadratic. The complex bands so obtained need to be unfolded onto the primitive Brillouin zone. In this paper, we present a unified method to unfold real and complex bands. Our method ensures that the measure associated with the projections of the non-primary wavefunction onto all candidate primary wavefunctions is invariant with respect to the energy E.     

The effect of respiratory oscillations in heart rate on detrended fluctuation analysis

Characterization of heart rate using detrended fluctuation analysis (DFA) is impeded by respiratory oscillations. In particular, the short-term exponent measured from 15 to 30 beats is compromised in the DFA. We reconstruct respiratory signal from electrocardiograms and attenuate the respiratory oscillation in the heart rate using a frequency-dependent subtraction approach. We validate this method by applying it to an electrocardiogram signal simulated using a coupled differential equation with the respiratory oscillation modelled using a sine function. The exponent estimated using the proposed approach agreed with the exponent incorporated in the model within a narrow range. In contrast, the exponent obtained from the raw data deviated from the expected value. Furthermore, the exponents obtained for the raw heart rate are smaller than the exponents obtained for the respiration oscillation attenuated heart rate. We apply this approach to heart rate measured from 12 preterm infants that were being treated for prematurity related complications. As observed in the simulated data, we show that compared to the raw heart rate, the respiratory oscillation attenuated heart rate shows higher short-term exponent (p < 0.001).     

Polymerization of coordinated monomers. XXII. Ab initio molecular orbital study on the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride as a model of growing radical end

The geometrical and electronic structures of the binary radical complexes of 2-methoxycarbonyl propyl radical with boron trichloride and with boron trifluoride were determined by using an ab initio molecular orbital method. The 2-methoxycarbonyl propyl radical complex was a model of the growing radical end in the copolymerization of methyl methacrylate in the presence of boron halides. The most stable structure of the binary radical complex composed of 2-methoxycarbonyl propyl radical with boron trichloride was a twisted form in which the dihedral angle between the vinyl group and the ester group was 32°, while that of the binary radical complex composed of methyl methacrylate radical with boron trifluoride was a planar form as the free radical. The frontier orbital energy of 2-methoxycarbonyl propyl radical was lowered by 0.06 au by the coordination of boron trichloride, while that was lowered only by 0.02 au by the coordination of boron trifluoride. The polymerization mechanism was elucidated on the basis of these predictions. © 1993 John Wiley & Sons, Inc.     

Electrochemical fluorination of chlorine-containing amines

The electrochemical fluorination of chlorine-containing alkylamines has been studied. It was found that, in general, the carbon-chlorine bond in the alkylamines is retained during electrochemical fluorination is anhydrous hydrogen fluoride, yielding chlorine-containing polyfluoroalkylamines. Perfluoroalkylamines and fluorocarbons were also produced.By the use of this method, several new chloropolyfluoroamines such as (CF₃)₂NCF₂CClF₂, (C₂F₅)₂NCF₂CClF₂, (CF₃)(C₂F₅)NCF₂CClF₂, (CClF₂CF₂)₂NCF₃, (CClF₂CF₂)₂NC₂F₅, (C₂F₅)(CClF₂CF₂)NF, (CClF₂CF₂)₂NF, (CF₃)₂NCF₂CF₂CClF₂, $\text{CF}{}_2\text{(CF}{}_2\text{)}{}_3\text{N}$CF₂CClF₂, and $\text{CF}{}_2\text{CF}{}_2\text{OC}{}_2\text{F}{}_4\text{N}$CF₂CClF₂ have been isolated and characterized.     

Solid Phase Extractive Preconcentration of Cobalt and Nickel in Hair Samples Using Ethyl Xanthate Modified Benzophenone

The ethyl xanthate complexes of cobalt and nickel are quantitatively retained on benzophenone in the pH range of 8.0–10.0. The solid mixture consisting of metal complex together with benzophenone is dissolved in 5mL of dimethyl formamide, and the cobalt and nickel contents were determined by flame atomic absorption spectrometry. The calibration graphs are rectilinear over the concentration range of 0–75 (Co) and 0–100 (Ni) µgL^–1. The detection limits of flame AAS for cobalt and nickel are lowered by a factor of 200 due to the solid phase extraction preconcentration procedure. NIES CRM Human Hair No. 5 and IAEA Reference Hair HH-1 certified reference materials were used in order to verify the accuracy of the developed preconcentration method in analysing human hair samples. The results obtained were found to be in excellent agreement with certified values. Furthermore, hair samples collected from various inhabitants of different age groups and sex living in the Indian states of Andhra Pradesh and Tamil Nadu were successfully analysed by flame AAS in conjunction with the solid phase extraction preconcentration procedure developed for cobalt and nickel.     

Rhodium Fluoroapatite Catalyzed Conjugate Addition of Arylboronic Acids to α,β‐Unsaturated Carbonyl Compounds

Rhodium fluoroapatite (RhFAP) is an efficient catalyst for conjugate addition of organoboron reagents to α,β‐unsaturated carbonyl compounds. A variety of arylboronic acids and α,β‐unsaturated carbonyl compounds were converted to the corresponding conjugate‐addition products, demonstrating the versatility of the reaction. The reaction is highly selective. RhFAP was recovered quantitatively by simple filtration, and reused for four cycles.