In this paper, the syntheses of kojic acid esters via chemical and enzymatic methods are
reviewed. The advantages and disadvantages of chemical process in term of process, safety and
efficiency are discussed. In enzymatic process, the significant process parameters related to the
synthesis of kojic acid esters such as the lipases, solvent, temperature and water content are
highlighted. Possible enzymatic synthesis using solvent and solvent-free system taking into
consideration of the difference in these systems involving cost, lipase reusability and efficiency
is comparatively reviewed. The possible approach for large scale production using various
enzyme reactor designs is also discussed and re-evaluated.
The transesterification of Thevetia peruviana seed oil with dimethyl carbonate (DMC) for preparing biodiesel has been studied using as an active catalyst potassium-methoxide (KOCH3). The effects of reaction conditions: Molar ratio of dimethyl carbonate to Thevetia peruviana seed oil, catalyst concentration, reaction time and agitation speed on dimethyl esters (DMC-Tp-BioDs) yield were investigated. The highest DMC-Tp-BioDs yield could reach 97.1% at refluxing temperature for 90 min with molar ratio of DMC-to-oil 5:1 and 2.0% w/w KOCH3 (based on oil weight). The fuel properties of the produced DMC-Tp-BioDs were compared with the ASTM D6751-02 biodiesel standard.
Interest in the medicinal properties of secondary metabolites of Boesenbergia rotunda (fingerroot ginger) has led to investigations into tissue culture of this plant. In this study, we profiled its primary and secondary metabolites, as well as hormones of embryogenic and non-embryogenic (dry and watery) callus and shoot base, Ultra Performance Liquid Chromatography-Mass Spectrometry together with histological characterization. Metabolite profiling showed relatively higher levels of glutamine, arginine and lysine in embryogenic callus than in dry and watery calli, while shoot base tissue showed an intermediate level of primary metabolites. For the five secondary metabolites analyzed (ie. panduratin, pinocembrin, pinostrobin, cardamonin and alpinetin), shoot base had the highest concentrations, followed by watery, dry and embryogenic calli. Furthermore, intracellular auxin levels were found to decrease from dry to watery calli, followed by shoot base and finally embryogenic calli. Our morphological observations showed the presence of fibrils on the cell surface of embryogenic callus while diphenylboric acid 2-aminoethylester staining indicated the presence of flavonoids in both dry and embryogenic calli. Periodic acid-Schiff staining showed that shoot base and dry and embryogenic calli contained starch reserves while none were found in watery callus. This study identified several primary metabolites that could be used as markers of embryogenic cells in B. rotunda, while secondary metabolite analysis indicated that biosynthesis pathways of these important metabolites may not be active in callus and embryogenic tissue.
The interest to sulfonated methyl esters of fatty acids (SME) has been growing during the last decade, because these surfactants are considered as an environmentally friendly and renewable alternative of the linear alkyl-benzene sulfonates (LAS). Here, we present a quantitative study on the properties of aqueous SME solutions, and especially on their surface tension isotherms, critical micelle concentration (CMC) and its dependence on the concentration of added NaCl. It is demonstrated that the CMC of an ionic surfactant determined by electrical conductivity is insensitive to the presence of a small nonionic admixture, so that the CMC values determined by conductivity represent the CMC of the pure surfactant. Using SME as an example, we have demonstrated the application of a new and powerful method for determining the physicochemical parameters of the pure ionic surfactant by theoretical data analysis ("computer purification") if the used surfactant sample contains nonionic admixtures, which are present as a rule. This method involves fits of the experimental data for surface tension and conductivity by a physicochemical model based on a system of mass-balance, chemical-equilibrium and electric-double-layer equations, which allows us to determine the adsorption and micellization parameters of C12-, C14-, C16- and C18-SME, as well the fraction of nonionic admixtures (if any). Having determined these parameters, we can further predict the interfacial and micellization properties of the surfactant solutions, such as surface tension, adsorption, degree of counterion binding, and surface electric potential at every surfactant, salt and co-surfactant concentrations.
Effect of isolated astaxanthin (ASX) and astaxanthin esters (ASXEs) from green microalga-Haematococcus pluvialis on hepatotoxicity and antioxidant activity against carbon tetrachloride (CCl4) induced toxicity in rats was compared with synthetic astaxanthin (SASX). ASX, ASXEs, and SASX, all dissolved in olive oil, fed to rats with 100 and 250 μg/kg b.w for 14 days. They were evaluated for their hepatoprotective and antioxidant activity by measuring appropriate enzymes. Among the treated groups, the SGPT, SGOT and ALP levels were decreased by 2, 2.4, and 1.5 fold in ASXEs treated group at 250 μg/Kg b.w. when compared to toxin group. Further, antioxidant enzymes catalase, glutathione, superoxide dismutase and lipid peroxidase levels were estimated in treated groups, their levels were reduced by 30-50 % in the toxin group, however these levels restored by 136.95 and 238.48 % in ASXEs treated group at 250 μg/kg. The lipid peroxidation was restored by 5.2 and 2.8 fold in ASXEs and ASX treated groups at 250 μg/kg. The total protein, albumin and bilirubin contents were decreased in toxin group, whereas normalized in ASXEs treated group. These results indicates that ASX and ASXEs have better hepatoprotection and antioxidant activity, therefore can be used in pharmaceutical and nutraceutical applications and also extended to use as food colorant.
A series of five new 2-(1-benzofuran-2-yl)-2-oxoethyl 4-(un/substituted)benzoates 4(a-e), with the general formula of C₈H₅O(C=O)CH₂O(C=O)C₆H₄X, X = H, Cl, CH₃, OCH₃ or NO₂, was synthesized in high purity and good yield under mild conditions. The synthesized products 4(a-e) were characterized by FTIR, ¹H-, (13)C- and ¹H-(13)C HMQC NMR spectroscopic analysis and their 3D structures were confirmed by single-crystal X-ray diffraction studies. These compounds were screened for their antimicrobial and antioxidant activities. The tested compounds showed antimicrobial ability in the order of 4b < 4a < 4c < 4d < 4e and the highest potency with minimum inhibition concentration (MIC) value of 125 µg/mL was observed for 4e. The results of antioxidant activities revealed the highest activity for compound 4e (32.62% ± 1.34%) in diphenyl-2-picrylhydrazyl (DPPH) radical scavenging, 4d (31.01% ± 4.35%) in ferric reducing antioxidant power (FRAP) assay and 4a (27.11% ± 1.06%) in metal chelating (MC) activity.
Methyl esters from vegetable oils have attracted a great deal of interest as substitute for petrodiesel to reduce dependence on imported petroleum and provide an alternate and sustainable source for fuel with more benign environmental properties. In the present study biodiesel was prepared from sunflower seed oil by transesterification by alkali-catalyzed methanolysis. The fuel properties of sunflower oil biodiesel were determined and discussed in the light of ASTM D6751 standards for biodiesel. The sunflower oil biodiesel was chemically characterized with analytical techniques like FT-IR, and NMR ((1)H and (13)C). The chemical composition of sunflower oil biodiesel was determined by GC-MS. Various fatty acid methyl esters (FAMEs) were identified by retention time data and verified by mass fragmentation patterns. The percentage conversion of triglycerides to the corresponding methyl esters determined by (1)H NMR was 87.33% which was quite in good agreement with the practically observed yield of 85.1%.
A total of 51 novel benzimidazoles were synthesized by a 4-step reaction starting from basic compound 4-fluoro-3-nitrobenzoic acid under relatively mild reaction conditions. The structure of the novel benzimidazoles was confirmed by mass spectra as well as (1)H NMR spectroscopic data. Out of the 51 novel synthesized compounds, 42 of them were screened for their antimycobacterial activity against Mycobacterium tuberculosis H37Rv strain using BacTiter-Glo™ Microbial Cell Viability (BTG) method. Results of activity screened using Alamar Blue method was also provided for comparison purposes. Two of the novel benzimidazoles synthesized showed moderately good activity with IC50 of less than 15 μM. Compound 5g, ethyl 2-(4-(trifluoromethyl)phenyl)-1-(2-morpholinoethyl)-1H-benzo[d]imidazole-5-carboxylate, was found to be the most active with IC50 of 11.52 μM.
Kojic acid is widely used to inhibit the browning effect of tyrosinase in cosmetic and food industries. In this work, synthesis of kojic monooleate ester (KMO) was carried out using lipase-catalysed esterification of kojic acid and oleic acid in a solvent-free system. Response Surface Methodology (RSM) based on central composite rotatable design (CCRD) was used to optimise the main important reaction variables, such as enzyme amount, reaction temperature, substrate molar ratio, and reaction time along with immobilised lipase from Candida Antarctica (Novozym 435) as a biocatalyst. The RSM data indicated that the reaction temperature was less significant in comparison to other factors for the production of a KMO ester. By using this statistical analysis, a quadratic model was developed in order to correlate the preparation variable to the response (reaction yield). The optimum conditions for the enzymatic synthesis of KMO were as follows: an enzyme amount of 2.0 wt%, reaction temperature of 83.69°C, substrate molar ratio of 1:2.37 (mmole kojic acid:oleic acid) and a reaction time of 300.0 min. Under these conditions, the actual yield percentage obtained was 42.09%, which is comparably well with the maximum predicted value of 44.46%. Under the optimal conditions, Novozym 435 could be reused for 5 cycles for KMO production percentage yield of at least 40%. The results demonstrated that statistical analysis using RSM can be used efficiently to optimise the production of a KMO ester. Moreover, the optimum conditions obtained can be applied to scale-up the process and minimise the cost.
Trimethylolpropane triesters are biodegradable synthetic lubricant base oil alternative to mineral oils, polyalphaolefins and diesters. These oils can be produced from trimethylolpropane (TMP) and fatty acid methyl esters via chemical or enzymatic catalyzed synthesis methods. In the present study, a commercial palm oil derived winter grade biodiesel (ME18) was evaluated as a viable and sustainable methyl ester source for the synthesis of high oleic trimethylolpropane triesters (HO-TMPTE). ME18 has fatty acid profile containing 86.8% oleic acid, 8.7% linoleic acid with the remaining minor concentration of palmitic acid, stearic acid and linolenic acid. It's high oleic property makes it superior to produce synthetic lubricant base oil that fulfills both the good low temperature property as well as good oxidative stability. The synthetic base oil produced had a viscosity of 44.3 mm(2)/s at 40°C meeting the needs for ISO 46 oils. It also exhibited an excellent viscosity index of 219 that is higher than some other commercial brands of trimethylolpropane trioleate. Properties of base oil such as cloud point, density, acid value, demulsibility and soap content were also examined. The oil was then used in the formulation of tapping oil and appraised in term of adaptability, stability and field test performance.
A series of N-ethyl phthalimide esters 4(a-n) were synthesized and characterized by spectroscopic studies. Further, the molecular structure of majority of compounds were analysed by single crystal X-ray diffraction studies. The X-ray analysis revealed the importance of substituents on the crystal stability and molecular packing. All the synthesized compounds were tested for in vitro antioxidant activity by DPPH radical scavenging, FRAP and CUPRAC methods. Few of them have shown good antioxidant activity.
The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.
Keriorrhoea is the involuntarily passing of orange oil per rectum. One of us (PMB) had the misfortune to experience this symptom, together with considerable gastrointestinal disturbances for a prolonged period of time after consumption of a deep sea fish, orange roughy, which is rich in liquid wax esters (LWEs). This paper presents a summary of available evidence concerned with the physiology and pathology of ingestion of LWEs, which can enter the human diet in substantial amounts from consumption of several species of deep-sea fish. LWEs are poorly digested and absorbed by the human body. They generally cause keriorrhoea when ingested deliberately or accidentally. Jojoba oil, which is a plant LWE, together with certain nutritional products (e.g. olestra) and medical (e.g. Orlistat) which are not LWEs may mimic the effects of LWEs, and cause similar gastrointestinal disturbances. This paper discusses the potential effects of LWEs as components of gastrointestinal micelles, and predicts that the orange oil which is leaked from a bout of keriorrhoea may contain considerable volumes of triacylglycerols (TAGs).
Biodiesel with improved yield was produced from microalgae biomass under simultaneous cooling and microwave heating (SCMH). Nannochloropsis sp. and Tetraselmis sp. which were known to contain higher lipid species were used. The yield obtained using this novel technique was compared with the conventional heating (CH) and microwave heating (MWH) as the control method. The results revealed that the yields obtained using the novel SCMH were higher; Nannochloropsis sp. (83.33%) and Tetraselmis sp. (77.14%) than the control methods. Maximum yields were obtained using SCMH when the microwave was set at 50°C, 800W, 16h of reaction with simultaneous cooling at 15°C; and water content and lipid to methanol ratio in reaction mixture was kept to 0 and 1:12 respectively. GC analysis depicted that the biodiesel produced from this technique has lower carbon components (<19 C) and has both reasonable CN and IV reflecting good ignition and lubricating properties.
Nannochloropsis sp. wet biomass was directly transesterified under microwave (MW) irradiation in the presence of methanol and various alkali and acid catalyst. Two different types of direct transesterification (DT) were used; one step and two step transesterification. The biodiesel yield obtained from the MWDT was compared with that obtained using conventional method (lipid extraction followed by transesterification) and water bath heating DT method. Findings revealed that MWDT efficiencies were higher compared to water bath heating DT by at least 14.34% and can achieve a maximum of 43.37% with proper selection of catalysts. The use of combined catalyst (NaOH and H2SO4) increased the yield obtained by 2.3-folds (water bath heating DT) and 2.87-folds (MWDT) compared with the one step single alkaline catalyst respectively. The property of biodiesel produced by MWDT has high lubricating property, good cetane number and short carbon chain FAME's compared with water bath heating DT.
In the study, the relationship between the quality and intensity of LED illumination with FAMEs produced were investigated. Nannochloropsis sp. was cultivated for 14 days under different intensities of 100, 150 and 200 μmol photons m(-2) s(-1) of red, blue and mixed red blue LED. The findings revealed that suitable combination of LED wavelengths and intensity; (red LED: 150, blue: 100 and mixed red blue: 200 μmol photons m(-2) s(-1)) produced maximum biomass growth and lipid content. It was observed that the quality and intensity of LED significantly influenced the composition of FAMEs. FAMEs produced under blue LED has high degree of unsaturation (DU) and low cetane number while those under red LED has low DU but higher CN. The combination of red blue LED has produced FAMEs with high ignition and lubricating property and also good oxidation stability indicated by the DU and CN values which lies midway between the red and blue.
The performance of gas chromatography (GC) combined with a hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) system for the determination of volatile and semi-volatile compounds in honey samples is evaluated. After headspace (HS) solid-phase microextraction (SPME) of samples, the accurate mass capabilities of the above system were evaluated for compounds identification. Accurate scan electron impact (EI) MS spectra allowed discriminating compounds displaying the same nominal masses, but having different empirical formulae. Moreover, the use of a mass window with a width of 0.005 Da provided highly specific chromatograms for selected ions, avoiding the contribution of interferences to their peak areas. Additional information derived from positive chemical ionization (PCI) MS spectra and ion product scan MS/MS spectra permitted confirming the identity of novel compounds. The above possibilities are illustrated with examples of honey aroma compounds, belonging to different chemical classes and containing different elements in their molecules. Examples of compounds whose structures could not be described are also provided. Overall, 84 compounds, from a total of 89 species, could be identified in 19 honey samples from 3 different geographic areas in the world. The suitability of responses measured for selected ions, corresponding to above species, for authentication purposes is assessed through principal components analysis.
Wavelength of light is a crucial factor which renders microalgae as the potential biodiesel. In this study, Tetraselmis sp. and Nannochloropsis sp. as famous targets were selected. The effect of different light wavelengths on growth rate and lipid production was studied. Microalgae were cultivated for 14 days as under blue, red, red-blue LED and white fluorescent light. The growth rate of microalgae was analyzed by spectrophotometer and cell counting while oil production under improved Nile red method. Optical density result showed the microalgae exhibited better growth curve under blue wavelength. Besides, Tetraselmis sp. and Nannochloropsis sp. under blue wavelength showed the higher growth rate (1.47 and 1.64 day(-1)) and oil production (102.954 and 702.366 a.u.). Gas chromatography analysis also showed that palmitic acid and stearic acid which were compulsory components for biodiesel contribute around 49-51% of total FAME from Nannochloropsis sp. and 81-83% of total FAME from Tetraselmis sp.
The use of pseudo-infinite methanol in increasing the rate of esterification and transesterification reactions was studied using oil palm trunk (OPT) and sugarcane bagasse (SCB) derived solid acid catalysts. The catalysts were prepared by incomplete carbonisation at 400°C for 8h, followed by sulfonation at 150°C for 15h and characterised using TGA/DTA, XRD, FT-IR, SEM-EDS, EA and titrimetric determinations of acid sites. Under optimal reaction conditions, the process demonstrated rapid esterification of palmitic acid, with FAME yields of 93% and 94% in 45min for OPT and SCB catalysts, respectively. With the process, moisture levels up to 16.7% accelerated the conversion of low FFA oils by sulfonated carbon catalysts, through moisture-induced violent bumping. Moisture assisted transesterification of palm olein containing 1.78% FFA and 8.33% added water gave FAME yield of 90% in 10h, which was two folds over neat oil.
This study aimed at examining the biophysical characteristics of human derived keratinocytes (HaCaT) cultured on cholesteryl ester liquid crystals (CELC). CELC was previously shown to improve sensitivity in sensing cell contractions. Characteristics of the cell integrin expressions and presence of extracellular matrix (ECM) proteins on the liquid crystals were interrogated using various immunocytochemical techniques. The investigation was followed by characterization of the chemical properties of the liquid crystals (LC) after immersion in cell culture media using Fourier transform infrared spectroscopy (FTIR). The surface morphology of cells adhered to the LC was studied using atomic force microscopy (AFM). Consistent with the expressions of the integrins α2, α3 and β1, extracellular matrix proteins (laminin, collagen type IV and fibronectin) were found secreted by the HaCaT onto CELC and these proteins were also secreted by cells cultured on the glass substrates. FTIR analysis of the LC revealed the existence of spectrum assigned to cholesterol and ester moieties that are essential compounds for the metabolizing activities of keratinocytes. The immunostainings indicated that cell adhesion on the LC is mediated by self-secreted ECM proteins. As revealed by the AFM imaging, the constraint in cell membrane spread on the LC leads to the increase in cell surface roughness and thickness of cell membrane. The biophysical expressions of cells on biocompatible CELC suggested that CELC could be a new class of biological relevant material.