New crystal structures of fully hydrogenated borophene (borophane) have been predicted by first principles calculation. Comparing with the chair-like borophane (C-boropane) that has been reported in literature, we obtained four new borophane conformers with much lower total-energy. The most stable one, washboard-like borophane (W-borophane), has energy about 113.41 meV/atom lower than C-borophane. In order to explain the relative stability of different borophane conformers, the atom configuration, density of states, charge transfer, charge density distribution and defect formation energy of B-H dimer have been calculated. The results show that the charge transfer from B atoms to H atoms is crucial for the stability of borophane. In different borophane conformers, the bonding characteristics between B and H atoms are similar, but the B-B bonds in W-borophane are much stronger than that in C-borophane or other structures. In addition, we examined the dynamical stability of borophane conformers by phonon dispersions and found that the four new conformers are all dynamically stable. Finally the mechanical properties of borophane conformers along an arbitrary direction have been discussed. W-borophane possesses unique electronic structure (Dirac cone), good stability and superior mechanical properties. W-borophane has broad perspective for nano electronic device.
A series of hydrogenated amorphous carbon (a-C:H) thin films were deposited using home-built direct-current (DC) plasma enhanced chemical vapour deposition (PECVD) system. In this present study, the a-C:H thin films were deposited using pure methane (CH4) gas diluted either with hydrogen (H) or helium (He). The effects of hydrogen and helium dilution on the photoluminescence (PL) properties and optical band gap (E04) were studied. The dependence of PL properties and optical energy gap on the film thickness has also been investigated. The characterization techniques used were optical transmission and photoluminescence spectroscopies. The sp2 cluster sizes were determined from Raman spectra are in the range of 5 to 7 nm. Hydrogen and helium dilution of methane strongly influences the PL efficiency of the a-C:H films. The PL efficiency are enhanced with increase in film thickness for a-C:H films prepared both from H and He diluted CH4. The optical energy gap of these films decreases with increase in H or He dilution and film thickness.
The incident involving hydrogen release in industry has become a major concern since numerous incidents were observed to have occured over the years. This paper is designed to do the consequence modelling and analysis using PHAST Simulator for the release rate, potential fire and vulnerability to human by lethality versus probit simulated at 5 mm, 35 mm and 70 mm leak scenarios and three types of atmospheric stability at hydrogenation plant in Telok Panglima Garang. The simulation was carried out by inputting data of leak scenario, meteorological data, material data and process data related to the hydrogenation plant. The simulation results were analyzed and discussed on the discharge rate, dispersion concentration and effect of jet fire such as flame length, downwind distance and lethality for radiation intensity level of 4 kW/m2 , 12.5 kW/m2 and 37.5 kW/m2 . Based on the results, the discharge rate and radiation intensity are dependent on the leak sizes regardless of the different atmospheric conditions. However, the dispersion is dependent on both atmospheric stability and leak sizes. Lastly, the lethality and area of impact are simulated from the radiation intensity produced by the jet fire for each leak size. To conclude, adoption of PHAST software is vital for consequence modelling as this software is able to illustrate the outcomes of hazards due to loss of containment and with this will enable related personnel to respond effectively to any hazardous incidents. As a recommendation, hydrogen fixed gas detectors are proposed for installations at specific location after taking into account the smallest leak that may happen which is at 5 mm leak size.
Quasi-homogeneous ligand-protected gold nanoclusters (Au NCs) with atomic precision and well-defined structure offer great opportunity for exploring the catalytic nature of nanogold catalysts at a molecular level. Herein, using real-time electrospray ionization mass spectrometry (ESI-MS), we have successfully identified the desorption and re-adsorption of p-mercaptobenzoic acid (p-MBA) ligands from Au25(p-MBA)18 NC catalysts during the hydrogenation of 4-nitrophenol in solution. This ligand dynamic (desorption and re-adsorption) would initiate structural transformation of Au25(p-MBA)18 NC catalysts during the reaction, forming a mixture of smaller Au NCs (Au23(p-MBA)16 as the major species) at the beginning of catalytic reaction, which could further be transformed into larger Au NCs (Au26(p-MBA)19 as the major species). The adsorption of hydrides (from NaBH4) is identified as the determining factor that could induce the ligand dynamic and structural transformation of NC catalysts. This study provides fundamental insights into the catalytic nature of Au NCs, including catalytic mechanism, active species and stability of Au NC catalysts during a catalytic reaction.
The lack of efficient hydrogen storage material is one of the bottlenecks for the large-scale implementation of hydrogen energy. Here, a series of new hydrogen storage materials, i.e., anilinide-cyclohexylamide pairs, are proposed via the metallation of an aniline-cyclohexylamine pair. DFT calculations show that the enthalpy change of hydrogen desorption (ΔHd) can be significantly tuned from 60.0 kJ per mol-H2 for the pristine aniline-cyclohexylamine pair to 42.2 kJ per mol-H2 for sodium anilinide-cyclohexylamide and 38.7 kJ per mol-H2 for potassium anilinide-cyclohexylamide, where an interesting correlation between the electronegativity of the metal and the ΔHd was observed. Experimentally, the sodium anilinide-cyclohexylamide pair was successfully synthesised with a theoretical hydrogen capacity of 4.9 wt%, and the hydrogenation and dehydrogenation cycle can be achieved at a relatively low temperature of 150 °C in the presence of commercial catalysts, in clear contrast to the pristine aniline-cyclohexylamine pair which undergoes dehydrogenation at elevated temperatures.
Using two different hydrosilylation methods, low temperature thermal and UV initiation, silicon (111) hydrogenated surfaces were functionalized in presence of an OH-terminated alkyne, a CF3-terminated alkyne and a mixed equimolar ratio of the two alkynes. XPS studies revealed that in the absence of premeditated surface radical through low temperature hydrosilylation, the surface grafting proceeded to form a Si-O-C linkage via nucleophilic reaction through the OH group of the alkyne. This led to a small increase in surface roughness as well as an increase in hydrophobicity and this effect was attributed to the surficial etching of silicon to form nanosize pores (~1-3 nm) by residual water/oxygen as a result of changes to surface polarity from the grafting. Furthermore in the radical-free thermal environment, a mix in equimolar of these two short alkynes can achieve a high contact angle of ~102°, comparable to long alkyl chains grafting reported in literature although surface roughness was relatively mild (rms = ~1 nm). On the other hand, UV initiation on silicon totally reversed the chemical linkages to predominantly Si-C without further compromising the surface roughness, highlighting the importance of surface radicals determining the reactivity of the silicon surface to the selected alkynes.
A combinative effect of two or more individual material properties, such as lattice parameters and chemical properties, has been well-known to generate novel nanomaterials with special crystal growth behavior and physico-chemical performance. This paper reports unusually high catalytic performance of AgPt nanoferns in the hydrogenation reaction of acetone conversion to isopropanol, which is several orders higher compared to the performance shown by pristine Pt nanocatalysts or other metals and metal-metal oxide hybrid catalyst systems. It has been demonstrated that the combinative effect during the bimetallisation of Ag and Pt produced nanostructures with a highly anisotropic morphology, i.e., hierarchical nanofern structures, which provide high-density active sites on the catalyst surface for an efficient catalytic reaction. The extent of the effect of structural growth on the catalytic performance of hierarchical AgPt nanoferns is discussed.
The effects of rf power on the structural properties of hydrogenated nanocrystalline silicon (nc-Si:H) thin films deposited using layer-by-layer (LbL) deposition technique in a home-built plasma enhanced chemical vapor deposition (PECVD) system were investigated. The properties of the films were characterized by X-ray diffraction (XRD), microRaman scattering spectroscopy, high resolution transmission electron microscope (HRTEM) and Fourier transform infrared (FTIR) spectroscopy. The results showed that the films consisted of different size of Si crystallites embedded within an amorphous matrix and the growth of these crystallites was suppressed at higher rf powers. The crystalline volume fraction of the films was optimum at the rf power of 60 W and contained both small and big crystallites
with diameters of 3.7 nm and 120 nm, respectively. The hydrogen content increased with increasing rf power and enhanced the structural disorder of the amorphous matrix thus decreasing the crystalline volume fraction of the films. Correlation of crystalline volume fraction, hydrogen content and structure disorder of the films under the effect of rf
power is discussed.
Inter-esterification is one of the processes used to modify the physico-chemical characteristics of oils and fats. Inter-esterification is an acyl-rearrangement reaction on the glycerol molecule. On the other hand, hydrogenation involves addition of hydrogen to the double bonds of unsaturated fatty acids. Due to health implications of trans fatty acids, which are formed during hydrogenation, the industry needs to find alternatives to hydrogenated fats. This paper discusses some applications of inter-esterified fats, with particular reference to inter-esterified palm products, as alternatives to hydrogenation. Some physico-chemical properties of inter-esterified fats used in shortenings are discussed. With inter-esterification, more palm stearin can be incorporated in vanaspati. For confectionary fats and infant formulations, enzymatic inter-esterification has been employed.
In recent years, issues regading safety and wellness of dietary oils and fats have received major attention. This is particularly so in the case of structured modified fats, which are being used extensively to meet the product-specific demand primarily in bakery industry as shortenings, cocoa butter substitutes in confectionary industry, and in margarine preparation, as butter substitute. During modification stages, native oils and fats are subjected to different physical and chemical treatments such as fractionation, hydrogenation and interesterification in order to produce fats with desirable
physical as well as functional properties. Numerous studies have demonstrated the adverse health effects of these modified oils and fats, especially trans fatty acids, using animal models as well as human volunteers. Consequently, the decadesold process of partial hydrogenation of oils has been abandoned in most nations. However, alternative technologies to hydrogenation are on rise, creating new trends in modified oils and fats synthesis to cater food industry needs that may have unforeseeable consequences on human health.
Papaya leaf methanolic extract (PLE) at concentrations of 0 (CON), 5 (LLE), 10 (MLE) and 15 (HLE) mg/250 mg dry matter (DM) with 30 mL buffered rumen fluid were incubated for 24 h to identify its effect on in vitro ruminal methanogenesis and ruminal biohydrogenation (BH). Total gas production was not affected (P > 0.05) by addition of PLE compared to the CON at 24 h of incubation. Methane (CH4 ) production (mL/250 mg DM) decreased (P
Nanostructured lipid carriers (NLC) composed of solid and liquid lipids, and surfactants are potentially good colloidal drug carriers. Before NLC can be used as drug carriers, the cytotoxicity of their components must be ascertained. The cytotoxicity of solid lipids (trilaurin, palmitin, docosanoid acid, and hydrogenated palm oil [HPO]) and surfactants (Polysorbate 20, 80, and 85) were determined on BALB/c 3T3 cells. The HPO and Polysorbate 80 were least cytotoxic and used with olive oil in the formulation of NLC. The particle size, polydispersity index, zeta potential, specific surface area, and crystallinity index of the NLC were 61.14 nm, 0.461, -25.4 mV, and 49.07 m(2) and 27.12% respectively, while the melting point was 4.3 °C lower than of HPO. Unlike in serum-free, NLC incubated in fetal bovine serum-supplemented medium did not show particle growth, suggesting that serum proteins in medium inhibit nanoparticles aggregation. The study also showed that NLC was less toxic to BALB/c 3T3 cells than Polysorbate 80. Thus, NLC with olive oil, HPO, and Polysorbate 80 as components are potentially good drug carriers with minimal cytotoxicity on normal cells.
Optimum processing conditions on palm oil-based formulations are required to produce the desired quality margarine. As oils and fats contribute to the overall property of the margarine, this paper will review the importance of beta' tending oils and fats in margarine formulation, effects of the processing parameters -- emulsion temperature, flow-rate, product temperature and pin-worker speed -- on palm oil margarines produced and their subsequent behaviour in storage. Palm oil, which contributes the beta' crystal polymorph and the best alternative to hydrogenated liquid fats, and the processing conditions can affect the margarine consistency by influencing the solid fat content (SFC) and the types of crystal polymorph formed during production as well as in storage. Palm oil, or hydrogenated palm oil and olein, in mixture with oils of beta tending, can veer the product to the beta' crystal form. However, merely having beta' crystal tending oils is not sufficient as the processing conditions are also important. The emulsion temperature had no significant effect on the consistency and polymorphic changes of the product during storage, even though differences were observed during processing. The consistency of margarine during storage was high at low emulsion flow-rates and low at high flow rates. The temperature of the scraped-surface tube-cooler is the most important parameter in margarine processing. High temperature will produce a hardened product with formation of beta-crystals during storage. The speed of the pin-worker is responsible for inducing crystallization but, at the same time, destroys the crystal agglomerates, resulting in melting.
Four formulations of burgers, prepared with 65% lean meat and 15% fat consisting of RBD palm stearin (PS), Socfat 4000P and Socfat 4100P and beef fat (BF) as control were evaluated for solid fat content (SFC), slip melting point (SMP), cooking loss, proximate analysis (moisture, fat and protein), colour, i.e. lightness ('L'), redness ('a') and yellowness ('b'), free fatty acid (FFA), iodine value (IV), thiobarbituric acid (TBA) and texture profile analysis (TPA). Sensory evaluation was carried out for texture, juiciness, aroma, oiliness and overall acceptance. SFC and SMP for raw and cooked SF4000P beef burgers were closest to BF control burgers, falling into the range of 35-40 degrees C. Cooking loss was highest for PS burgers, there were no significant differences (P > 0.05) amongst BF, SF4000P and SF4100P burgers. Proximate analysis on raw burgers showed SF4000P to contain high fat and lowest moisture contents. Objective textural measurements using texture profile analysis (TPA) for all cooked burgers showed no significant differences (P > 0.05) for springiness and cohesiveness. Variation of values among the formulations for hardness, gumminess and chewiness are explained by the differences of SFC for beef burgers with various types of fats. Raw and cooked PS burgers have the lightest 'L' values compared with other fat-substituted burgers while BF, SF4000P and SF4100P indicated no significant differences (P > 0.05) for 'L', 'a' and 'b' values. Beef fat showed the highest amount of free fatty acids (FFA) compared to palm oil samples. For the iodine value (IV), SF4000P showed the highest value which means that it contained the highest level of unsaturated fatty acids followed by PS, BF and SF4100P successively. SF4000P had the highest TBA values followed successively by BF, PS and SF4100P. For sensory evaluation, PS burgers had the least oily taste. This may be due to its high cooking loss. Taste panelists could not differentiate burgers with substituted vegetable fats against the control burgers.
Catalytic hydrogenation of carbon dioxide (CO2) to methanol is an attractive way to recycle and utilize CO2. A series of Cu/ZnO/Al2O3/ZrO2 catalysts (CZAZ) containing different molar ratios of Cu/Zn were prepared by the co-precipitation method. The catalysts were characterized by temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive x-ray analysis (FESEM-EDX) and X-ray diffraction (XRD). Higher surface area, SABET values (42.6-59.9 m2/g) were recorded at low (1) and high (5) Cu/Zn ratios with the minimum value of 35.71 m2/g was found for a Cu/Zn of 3. The reducibility of the metal oxides formed after calcination of catalyst samples was also affected due to change in metal-support interaction. At a reaction temperature of 443 K, total gas pressure of 3.0 MPa and 0.1 g/mL of the CZAZ catalyst, the selectivity to methanol decreased as the Cu/Zn molar ratio increased, and the maximum selectivity of 93.9 was achieved at Cu/Zn molar ratio of 0.33. With a reaction time of 3h, the best performing catalyst was CZAZ75 with Cu/Zn molar ratio of 5 giving methanol yield of 6.4%.
A variety of modified fats that provide different functionalities are used in processed foods to optimize product characteristics and nutrient composition. Partial hydrogenation results in the formation of trans FAs (TFAs) and was one of the most widely used modification processes of fats and oils. However, the negative effects of commercially produced TFAs on serum lipoproteins and risk for cardiovascular disease resulted in the Institute of Medicine and the 2010 US Dietary Guidelines for Americans both recommending that TFA intake be as low as possible. After its tentative 2013 determination that use of partially hydrogenated oils is not generally regarded as safe, the FDA released its final determination of the same in 2015. Many food technologists have turned to interesterified fat as a replacement. Interesterification rearranges FAs within and between a triglyceride molecule by use of either a chemical catalyst or an enzyme. Although there is clear utility of interesterified fats for retaining functional properties of food, the nutrition and health implications of long-term interesterified fat consumption are less well understood. The Technical Committee on Dietary Lipids of the North American Branch of the International Life Sciences Institute sponsored a workshop to discuss the health effects of interesterified fats, identify research needs, and outline considerations for the design of future studies. The consensus was that although interesterified fat production is a feasible and economically viable solution for replacing dietary TFAs, outstanding questions must be answered regarding the effects of interesterification on modifying certain aspects of lipid and glucose metabolism, inflammatory responses, hemostatic parameters, and satiety.
Different solvents (hexane, chloroform, ethyl acetate, butanol, and water) were used to identify the effect of papaya leaf (PL) fractions (PLFs) on ruminal biohydrogenation (BH) and ruminal methanogenesis in an in vitro study. PLFs at a concentration of 0 (control, CON) and 15 mg/250 mg dry matter (DM) were mixed with 30 mL of buffered rumen fluid and were incubated for 24 h. Methane (CH4) production (mL/250 mg DM) was the highest (P < 0.05) for CON (7.65) and lowest for the chloroform fraction (5.41) compared to those of other PLFs at 24 h of incubation. Acetate to propionate ratio was the lowest for PLFs compared to that of CON. Supplementation of the diet with PLFs significantly (P < 0.05) decreased the rate of BH of C18:1n-9 (oleic acid; OA), C18:2n-6 (linoleic acid; LA), and C18:3n-3 (α-linolenic acid; LNA) compared to that of CON after 24 h of incubation. Real time PCR indicated that total protozoa and total methanogen population in PLFs decreased (P < 0.05) compared to those of CON.
Lipid is the general name given to fats and oils, which are the basic components of cooking oils, shortening, ghee, margarine, and other edible fats. The chosen term depends on the physical state at ambient temperature; fats are solids and oils are liquids. The chemical properties of the lipids, including degree of saturation, fatty acid chain length, and acylglycerol molecule composition are the basic determinants of physical characteristics such as melting point, cloud point, solid fat content, and thermal behavior. This review will discuss the major lipid modification strategies, hydrogenation, and chemical and enzymatic interesterification, describing the catalysts used mechanisms, kinetics, and impacts on the health-related properties of the final products. Enzymatic interesterification will be emphasized as method that produces a final product with good taste, zero trans fatty acids, and a low number of calories, requires less contact with chemicals, and is cost efficient.
Partial hydrogenation of oil results in fats containing unusual isomeric fatty acids characterized by cis and trans configurations. Hydrogenated fats containing trans fatty acids increase plasma total cholesterol (TC) and LDL-cholesterol while depressing HDL-cholesterol levels. Identifying the content of trans fatty acids by food labeling is overshadowed by a reluctance of health authorities to label saturates and trans fatty acids separately. Thus, it is pertinent to compare the effects of trans to saturated fatty acids using stable isotope methodology to establish if the mechanism of increase in TC and LDL-cholesterol is due to the increase in the rate of endogenous synthesis of cholesterol. Ten healthy normocholesterolemic female subjects consumed each of two diets containing approximately 30% of energy as fat for a fourweek period. One diet was high in palmitic acid (10.6% of energy) from palm olein and the other diet exchanged 5.6% of energy as partially hydrogenated fat for palmitic acid. This fat blend resulted in monounsaturated fatty acids decreasing by 4.9 % and polyunsaturated fats increasing by 2.7%. The hydrogenated fat diet treatment provided 3.1% of energy as elaidic acid. For each dietary treatment, the fractional synthesis rates for cholesterol were measured using deuterium-labeling procedures and blood samples were obtained for blood lipid and lipoprotein measurements. Subjects exhibited a higher total cholesterol and LDL-cholesterol level when consuming the diet containing trans fatty acids while also depressing the HDL-cholesterol level. Consuming the partially hydrogenated fat diet treatment increased the fractional synthesis rate of free cholesterol. Consumption of hydrogenated fats containing trans fatty acids in comparison to a mixtur e of palmitic and oleic acids increase plasma cholesterol levels apparently by increasing endogenous synthesis of cholesterol.
A new, effective one-pot synthesis of the 6, N2-diaryl-1,3,5-triazine-2,4-diamines under microwave irradiation was developed. The method involved an initial three-component condensation of cyanoguanidine, aromatic aldehydes, and arylamines in the presence of hydrochloric acid. Without isolation, the resulting 1,6-diaryl-1,6-dihydro-1,3,5-triazine-2,4-diamines were treated with a base to initiate Dimroth rearrangement and spontaneous dehydrogenative aromatization, affording the desired compounds. The developed method was found to be sufficiently general in scope, tolerating various aromatic aldehydes and amines; by using their combinations in the first step, a representative library of 110 compounds was successfully prepared and screened for anticancer properties.