Application of supercritical fluid chromatography in the quantitative analysis of minor components (carotenes,vitamin E,sterols, and squalene) from palm oil

The application of supercritical fluid chromatography (SFC) coupled with a UV variable-wavelength detector to isolate the minor components (carotenes, vitamin E, sterols, and squalene) in crude palm oil (CPO) and the residual oil from palm-pressed fiber is reported. SFC is a good technique for the isolation and analysis of these compounds from the sources mentioned. The carotenes, vitamin E, sterols, and squalene were isolated in less than 20 min. The individual vitamin E isomers present in palm oil were also isolated into their respective components, α-tocopherol, α-tocotrienol, γ-tocopherol, γ-tocotrienol, and δ-tocotrienol. Calibration of all the minor components of palm as well as the individual components of palm vitamin E was carried out and was found to be comparable to those analyzed by other established analytical methods.     

Simultaneous quantification of free fatty acids,free sterols,squalene, and acylglycerol molecular species in palm oil by high-temperature gas chromatography-flame ionization detection

This paper discusses a rapid GC-FID technique for the simultaneous quantitative analysis of FFA, MAG, DAG, TAG, sterols, and squalene in vegetable oils, with special reference to palm oil. The FFA content determined had a lower SE compared with a conventional titrimetric method. Squalene and individual sterols, consisting of β-sitosterol, stigmasterol, campesterol, and cholesterol, were accurately quantified without any losses. This was achieved through elimination of tedious conventional sample pretreatments, such as saponification and preparative TLC. With this technique, the separation of individual MAG, consisting of 16∶0, 18∶0, and 18∶1 FA, and the DAG species, consisting of the 1,2(2,3)- and 1,3-positions, was sufficient to enable their quantification. This technique enabled the TAG to be determined according to their carbon numbers in the range of C₄₄ to C₅₆. Comparisons were made with conventional methods, and the results were in good agreement with those reported in the literature.     

Separation of He/N2/CH4 ternary mixtures by a triple-reflux pressure swing adsorption process

Conventional pressure swing adsorption (PSA) processes can only produce one high purity product in a single stage, whereas the state-of-art dual-reflux PSA (DR-PSA) can produce two high purity products simultaneously. However, multicomponent gas separation is often required in the industry, targeting at recovering several valued products at the same time. In this study, we propose a novel adsorption process, namely triple-reflux PSA (TR-PSA), to separate three components simultaneously. A middle product outlet and a middle reflux stream were introduced to the adsorption columns of a conventional DR-PSA process to separate ternary mixtures of nitrogen, methane, and helium. Nonisothermal dynamic models were built to investigate the impacts of operating parameters particularly the location of the middle reflux/product stream and the middle reflux flow rates. Results showed that the TR-PSA process successfully separated ternary mixtures obtaining three enriched products simultaneously in a single stage, yielding a separation performance comparable to that of the double-stage DR-PSA with significantly lower capital and energy cost.     

P450 BM3 Monooxygenase as an Efficient NAD(P)H‐Oxidase for Regeneration of Nicotinamide Cofactors in ADH‐Catalysed Preparative Scale Biotransformations

Enzymatic oxidations of primary and secondary alcohols catalysed by nicotinamide dependent alcohol dehydrogenases on the preparative scale require cofactor regeneration systems. Of critical value from an economic and ecological perspective is the application of NAD(P)H‐oxidases, which utilise molecular oxygen as a cost‐effective, atom‐efficient and environmentally benign oxidant to regenerate the cofactor NAD(P)⁺. Herein, the P450 BM3 monooxygenase from Bacillus megaterium is presented as an NAD(P)H‐oxidase for the successful regeneration of both NADP⁺ and NAD⁺ on the preparative scale. This enzyme was exemplarily applied for ADH‐catalysed oxidative kinetic resolutions of racemic secondary alcohols and the desymmetrisation of a meso‐diol leading to enantiomerically enriched secondary alcohols in both cases. Furthermore, the ADH‐catalysed oxidation of a primary alcohol targeting the corresponding aldehyde was performed. The obtained results significantly broaden the scope of feasible oxidative biotransformations, thereby increasing the number of synthetic reactions complying with key challenges of a modern and sustainable chemistry such as mild reaction conditions, environmentally benign solvents, and biodegradable non‐toxic catalysts.

     

Effect of temperature on sulfur-doped diamond-like carbon films deposited by pulsed laser ablation

In this study, S-DLC films were deposited using pulsed laser ablation of a novel sulfur-graphite (SG) mixture target using an ArF excimer laser (193 nm). The SG targets were made by mixing sulfur and graphite powders at different sulfur molar percentages from 0% to 25%. The S-DLC films were deposited at room temperature, 150 °C and 250 °C. The optical and electronic properties of the doped films were studied. Laser Raman spectroscopy indicated increased graphitic behavior with temperature but decreased with higher sulfur content. Spectroscopic ellipsometry analyses found that the optical band-gap energy, extinction coefficient and reflective index, clearly depended on deposition temperature and sulfur content. Hall Effect measurements indicated n-type carrier with concentration in the range of 1 × 10¹⁴ to 2 × 10¹⁷ cm^− 3, strongly depended upon the deposition temperature and amount of sulfur.     

Effect of Eu-implantation and annealing on the GaN quantum dots excitonic recombination

Undoped self-assembled GaN quantum dots (QD) stacked in superlattices (SL) with AlN spacer layers were submitted to thermal annealing treatments. Changes in the balance between the quantum confinement, strain state of the stacked heterostructures and quantum confined Stark effect lead to the observation of GaN QD excitonic recombination above and below the bulk GaN bandgap. In Eu-implanted SL structures, the GaN QD recombination was found to be dependent on the implantation fluence. For samples implanted with high fluence, a broad emission band at 2.7 eV was tentatively assigned to the emission of large blurred GaN QD present in the damage region of the implanted SL. This emission band is absent in the SL structures implanted with lower fluence and hence lower defect level. In both cases, high energy emission bands at approx. 3.9 eV suggest the presence of smaller dots for which the photoluminescence intensity was seen to be constant with increasing temperatures. Despite the fact that different deexcitation processes occur in undoped and Eu-implanted SL structures, the excitation population mechanisms were seen to be sample-independent. Two main absorption bands with maxima at approx. 4.1 and 4.7 to 4.9 eV are responsible for the population of the optically active centres in the SL samples.     

Advanced chemically induced phase separation in thermosets: Polybenzoxazines toughened with multifunctional thermoplastic main-chain benzoxazine prepolymers

Multifunctional thermoplastic main-chain benzoxazine prepolymers were synthesized and systematically varied in their structure in order to function as high-performance toughener additives. Their unique chemical composition allows multiple covalent crosslinking with many thermoset network systems including benzoxazines and epoxides in conjunction with a defined chemical induced phase separation (CIPS) upon curing. This was successfully shown using a benzoxazine-based thermoset resin matrix as an example. The corresponding morphologies were addressable in a predictable manner and brought into context with the obtained macroscopic mechanical and thermal properties. In this relationship the CIPS process was classified and compared with the literature in more general means for advanced morphology control by differentiating between covalently attached and so-called gradient domain structures. The prepolymers were characterized by ¹H NMR, FT-IR, DSC and TGA. The thermoset morphologies were investigated by TEM and AFM. The fracture toughness (K_Ic) and the elastic modulus (E) were measured by fracture and three point bending experiments. Thermal properties of the resulting films have been tested by DMA.     

Comparison of ionic liquid,acid and alkali pretreatments for sugarcane bagasse enzymatic saccharification

BACKGROUND: Much attention has been given to applying ionic liquids (ILs) as an alternative pretreatment method for lignocellulosic biomass. This study aims to select the most suitable type of IL for pretreating sugarcane bagasse (SCB). The potential of ILs for pretreatment was evaluated and compared with conventional pretreatment media, acids and alkalis. The performance of the pretreatment media was evaluated based on the amount of reducing sugar produced from enzymatic saccharification, the energy requirement, and changes in the chemical structure and crystallinity index of the pretreated bagasse. RESULTS: 1‐ethyl‐3‐methylimidazolium acetate [EMIM]oAc was selected as the most suitable IL for SCB pretreatment. The optimum yields of reducing sugar obtained from [EMIM]oAc‐, alkali‐, and acid‐pretreated SCB were 69.5%, 92.8% and 41.3%, respectively. Although a lower yield of reducing sugar was obtained, [EMIM]oAc pretreatment required the least energy to pretreat 1 kg of SCB. Moreover, the percentage of SCB loss during [EMIM]oAc pretreatment was the lowest. [EMIM]oAc‐pretreated SCB also had the lowest crystallinity index (CI) with the most amorphous structure. CONCLUSION: [EMIM]oAc appears to be another option for pretreating SCB, and other issues such as the recyclability of [EMIM]oAc is worth investigating. Copyright © 2011 Society of Chemical Industry     

Effect of coupling agent content on properties of composites made from polylactic acid and chrysanthemum waste

Chrysanthemum flower is among one of the highly sought after and widely planted flower crops, in particular for cultural and religious ceremonies. However, the chrysanthemum stem and stalk have little value and usually discard as by‐product waste from floristry. The objective of this research is to investigate the potential value of utilizing chrysanthemum stem and stalk as reinforcing fillers for thermoplastic composites. In this study, 2‐mm thick composite sheet containing predefined formulations of polylactic acid (PLA), chrysanthemum waste filler (CWF) ranging from 15 to 60 phr, and maleated polyethylene (MAPE) coupling agent up to 5 phr were prepared with the aid of Haake internal mixer and compression molding. The effect of MAPE loading on tensile, thermal, and morphological properties of PLA/CWF composites was investigated. The findings revealed that PLA/CWF composite attained improved tensile modulus compared to the neat PLA, and the tensile modulus increases with higher concentration of CWF. However, both tensile strength and elongation at break reduces with increase loading of CWF. Overall, PLA/CWF composites with MAPE shows better performance compared to those without MAPE, where an optimum strength of 21.8 MPa can be achieved with 60 phr CW and 3 phr MAPE. The measured tensile strength is comparable to alternatives natural fiber thermoplastic composites demonstrating its potential to be used in non‐structurally demanding application. J. VINYL ADDIT. TECHNOL., 26:10–16, 2020. © 2019 Society of Plastics Engineers