Transesterification via Parametric Modelling and Optimization of Marula (Sclerocarya birrea) Seed Oil Methyl Ester Synthesis.

This study investigates Marula (Sclerocarya birrea) seed oil (SBSO) as a novel feedstock for biodiesel production through the transesterification process catalysed by heterogeneous bio-alkali derived from banana (Musa acuminata) peels. Response surface methodology (RSM) and artificial neural network (ANN) tools were used for the modelling and optimization of the process variables. The reaction process parameters considered were methanol/SBSO molar ratio, catalyst loading levels, reaction time and temperature. Central composite design (CCD) was espoused to generate 30 experimental conditions which were deployed in investigating the individual and synergetic effect of the process input variables on Sclerocarya birrea oil methyl ester (SBOME) yield. Appropriate statistical indices were adopted to investigate the predictive aptitude of the two models. Analysis shows that ANN model obtained for the transesterification process has a higher coefficient of determination (R2) of 0.9846 and lower absolute average deviation (AAD) of 0.07% compared to RSM model with R2 of 0.9482 and AAD of 0.12%. The process modelling outcome also confirmed ANN performance to be more precise than RSM. At methanol/SBSO ratio of 6:1, catalyst loading level of 2 wt%, process reaction time of 50 min and temperature of 55°C, the experimental maximum SBOME yield was observed to be 96.45 wt % following the ANN predicted yield of 96.45 wt % and RSM predicted yield of 96.65 wt % respectively. The analysed fuel properties of SBOME was found satisfactory within the biodiesel stipulated standard limit(s). The study establishes that SBSO is a good source for biodiesel production and its biodiesel methyl ester is a potential substitute for petroleum diesel and a bioenergy fuel.

Comprehensive utilization of glycerol from sugarcane bagasse pretreatment to fermentation.

In this study, the effects of glycerol pretreatment on subsequent glycerol fermentation and biomass fast pyrolysis were investigated. The liquid fraction from the pretreatment process was evaluated to be feasible for fermentation by Paenibacillus polymyxa and could be an economic substrate. The pretreated biomass was further utilized to obtain levoglucosan by fast pyrolysis. The pretreated sugarcane bagasse exhibited significantly higher levoglucosan yield (47.70%) than that of un-pretreated sample (11.25%). The promotion could likely be attributed to the effective removal of alkali and alkaline earth metals by glycerol pretreatment. This research developed an economically viable manufacturing paradigm to utilize glycerol comprehensively and enhance the formation of levoglucosan effectively from lignocellulose.

Novel Pendant Benzene Disulfonic Acid Blended SPPO Membranes for Alkali Recovery: Fabrication and Properties.

To reconcile the trade-off between separation performance and availability of desired material for cation exchange membranes (CEMs), we designed and successfully prepared a novel sulfonated aromatic backbone-based cation exchange precursor named sodium 4,4'-(((((3,3'-disulfo-[1,1'-biphenyl]-4,4'-diyl)bis(oxy)) bis(4,1-phenylene))bis(azanediyl))bis(methylene))bis(benzene-1,3-disulfonate) [DSBPB] from 4,4'-bis(4-aminophenoxy)-[1,1'-biphenyl]-3,3'-disulfonic acid [BAPBDS] by a three-step procedure that included sulfonation, Michael condensation followed by reduction. Prepared DSBPB was used to blend with sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) to get CEMs for alkali recovery via diffusion dialysis. Physiochemical properties and electrochemical performance of prepared membranes can be tuned by varying the dosage of DSBPB. All the thermo-mechanical properties like DMA and TGA were investigated along with water uptake (WR), ion exchange capacity (IEC), dimensional stability, etc. The effect of DSBPB was discussed in brief in connection with alkali recovery and ion conducting channels. The SPPO/DSBPB membranes possess both high water uptake as well as ion exchange capacity with high thermo-mechanical stability. At 25 °C the dialysis coefficients (UOH) appeared to be in the range of 0.0048-0.00814 m/h, whereas the separation factor (S) ranged from 12.61 to 36.88 when the membranes were tested for base recovery in Na2WO4/NaOH waste solution. Prepared membranes showed much improved DD performances compared to traditional SPPO membrane and possess the potentiality to be a promising candidate for alkali recovery via diffusion dialysis.

How Does Alkali Aid Protein Extraction in Green Tea Leaf Residue: A Basis for Integrated Biorefinery of Leaves.

Leaf protein can be obtained cost-efficiently by alkaline extraction, but overuse of chemicals and low quality of (denatured) protein limits its application. The research objective was to investigate how alkali aids protein extraction of green tea leaf residue, and use these results for further improvements in alkaline protein biorefinery. Protein extraction yield was studied for correlation to morphology of leaf tissue structure, protein solubility and hydrolysis degree, and yields of non-protein components obtained at various conditions. Alkaline protein extraction was not facilitated by increased solubility or hydrolysis of protein, but positively correlated to leaf tissue disruption. HG pectin, RGII pectin, and organic acids were extracted before protein extraction, which was followed by the extraction of cellulose and hemi-cellulose. RGI pectin and lignin were both linear to protein yield. The yields of these two components were 80% and 25% respectively when 95% protein was extracted, which indicated that RGI pectin is more likely to be the key limitation to leaf protein extraction. An integrated biorefinery was designed based on these results.

Decontamination of metals, pentachlorophenol, and polychlorined dibenzo-p-dioxins and dibenzofurans polluted soil in alkaline conditions using an amphoteric biosurfactant.

In this paper, flotation in acidic conditions and alkaline leaching soil washing processes were compared to decontaminate four soils with variable contamination with metals, pentachlorophenol (PCP), and polychlorodibenzo dioxins and furans (PCDD/F). The measured concentrations of the four soils prior treatment were between 50 and 250 mg/kg for As, 35 and 220mg/kg for Cr, 80 and 350mg/kg for Cu, and 2.5 and 30mg/kg for PCP. PCDD/F concentrations reached 1394, 1375, 3730, and 6289ng/kg for F1, S1, S2, and S3 soils, respectively. The tests were carried out with masses of 100g of soil (fraction 0-2 mm) in a 2 L beaker or in a 1 L flotation cell. Soil flotation in sulphuric acid for 1 h at 60 degreeC with three flotation cycles using the surfactant cocamidopropyl betaine (BW) at 1% allows the solubilization of metals and PCP with average removal yields of 85%, 51%, 90%, and 62% for As, Cr, Cu, and PCP, respectively. The alkaline leaching for 2 h at 80 degreeC solubilizes As, Cr, Cu, and PCP with average removal yields of 60%, 32%, 77%, and 87%, respectively. Tests on PCDD/F solubilization with different surfactants were carried out in combination with the alkaline leaching process. PCDD/F removal yields of 25%, 72%, 70%, and 74% for F1, S1, S2, and S3 soils, respectively, were obtained using the optimized conditions.

Approaches to find complementary separation conditions for resolving complex mixtures by high-performance liquid chromatography.

Chromatographic problems are usually addressed trying to find out a single experimental condition aimed to resolve all compounds in the sample. However, very often, the chromatographic system is not able to provide full resolution. When a separation fails, the usual choice is introducing a drastic change in the chromatographic system (e.g. column, solvent, pH). There are, however, other possibilities that take advantage of the gathered information in the failed separation, without the need of new experiments, based on the concept of complementary separations (e.g. isocratic mobile phases, gradients, columns, chromatographic modes). One separation condition will focus on the resolution of some compounds in the sample, while the other compounds will be resolved using a second (or subsequent) condition(s). Complementary separations, being a simple and attractive idea, present, however, challenges in terms of computation volume and complexity of the required algorithms. This work describes in detail different approaches that have been developed up-to-date for this purpose, and introduces a new approach based on the peak count concept that is benefited of the best features of the previous approaches: high reliability in finding the solution, accessibility to analysts without specialised programming skills and short computation time.

Adsorption of acids and bases from aqueous solutions onto silicon dioxide particles.

The adsorption of acids and bases onto the surface of silicon dioxide (SiO(2)) particles was systematically studied as a function of several variables, including activation conditions, contact time, specific surface area, particle size, concentration and temperature. The physical properties of SiO(2) particles were investigated, where characterizations were carried out by FT-IR spectroscopy, and morphology was examined by scanning electron microscopy (SEM). The SEM of samples showed good dispersion and uniform SiO(2) particles with an average diameter of about 1-1.5 microm. The adsorption results revealed that SiO(2) surfaces possessed effective interactions with acids and bases, and greatest adsorption capacity was achieved with NaOH, where the best fit isotherm model was the Freundlich adsorption model. The adsorption properties of raw SiO(2) particles were further improved by ultrasonication. Langmuir monolayer adsorption capacity of NaOH adsorbate at 25 degrees C on sonicated SiO(2) (182.6 mg/g) was found to be greater than that of the unsonicated SiO(2) (154.3mg/g). The spontaneity of the adsorption process was established by decreases in DeltaG(ads)(0), which varied from -10.5 to -13.6 kJ mol(-1), in the temperature range 283-338K.

Using subcritical/supercritical fluid chromatography to separate acidic, basic, and neutral compounds over an ionic liquid-functionalized stationary phase.

We packed an ionic liquid (IL)-functionalized stationary phase--based on 1-octyl-3-propylimidazolium chloride covalently bounded to silica gel--into a 3.2mmx250mm column for the simultaneous separation of acidic, basic, and neutral compounds using carbon dioxide subcritical/supercritical fluid chromatography (SFC), and examined the effects of the pressure, temperature, co-solvents, and additives on the retention behavior of the analytes. The model compounds tested for SFC separation are acetaminophen, metoprolol, fenoprofen, ibuprofen, naphthalene, and testosterone. The data indicate that hydrogen-bonding and hydrophobic interactions between the analytes and the IL-modified stationary phase seem to involve in the separation process. Simultaneous separation of acidic, basic, and neutral compounds via SFC was successful at a co-solvent content of 20% MeOH, a pressure of 110 bar, and a column temperature of 35 degrees C. The relative standard deviations of the retention times and peak areas at 50 ppm were all less than 4 and 8% (n=6), respectively.

Removal of basic (Methylene Blue) and acid (Egacid Orange) dyes from waters by sorption on chemically treated wood shavings.

Spruce wood shavings from Picea abies were used for an adsorptive removal of both basic as well as acid dyes from waters. The sorption properties of the sorbents were modified with HCl, Na(2)CO(3) and Na(2)HPO(4). The treatment of the wood sorbents with alkaline carbonate solution as well as with phosphate solution increased the sorption ability for the basic dye (Methylene Blue), whereas the treatment with mineral acid decreased the sorption ability for Methylene Blue to some extent. The opposite is true for the sorption of the acid dye--Egacid Orange. The maximum sorption capacities estimated from the Langmuir-Freundlich isotherms ranged from 0.060 to 0.165 mmol g(-1) for Methylene Blue, and from 0.045 to 0.513 mmol g(-1) for Egacid Orange. The basic dye sorption decreased at low pH values in accordance with a presupposed ion-exchange mechanism of the sorption. The sorption of acid dye, on the other hand, decreased with increasing pH. The presence of inorganic salts as well as surfactants exhibited only minor effects on the dye sorption.

Optimization of extracellular psychrophilic alkaline lipase produced by marine Pseudomonas sp. (MSI057).

An endosymbiotic Pseudomonas sp. (MSI057), which could produce high yields of lipase, was isolated from marine sponge Dendrilla nigra, collected from the peninsular coast of India. Maximum production of enzyme was obtained in minimal medium supplemented with 1% tributyrin. Catabolite repression was observed when the medium was supplemented with readily available carbon sources. The optimum temperature and pH for the enzyme production was 30 degrees C and 9.0, respectively. The enzyme exhibited maximum activity in pH range of 8-9 with an optimum pH 9.0. The activity of purified enzyme was optimum at 37 degrees C and showed 80% activity at 20 degrees C and the enzyme activity decreased dramatically above 50 degrees C. Based on the present findings, the enzyme was characterized as psychrophilic alkaline lipase, which can be developed for industrial applications.

Chromatographic resolution of a salt into its parent acid and base constituents.

Based on the results of the earlier proposed process of separation of mixtures of mineral electrolytes by size-exclusion chromatography (SEC), it has been suggested that a mineral salt must spontaneously resolve, at least partially, into its parent acid and base constituents, provided that the separating media discriminates the anion and cation of the salt according to their size. Indeed, migration of a zone of an aqueous salt solution through a bed of neutral nanoporous hypercrosslinked polystyrene-type packing was shown to result in the generation of acidic and alkaline effluent fractions. The principle of spontaneous salt resolution has been extended to other types of discriminating interactions between the stationary phase and the two ions of the salt. The idea was exemplified by the resolution of ammonium acetate, due to hydrophobic retention of the acetate, into fractions enriched in ammoniac and then acetic acid.

Optimal conditions for alkaline detoxification of dilute-acid lignocellulose hydrolysates.

Alkaline detoxification strongly improves the fermentability of dilute-acid hydrolysates in the production of bioethanol from lignocellulose with Saccharomyces cerevisiae. New experiments were performed with NH4OH and NaOH to define optimal conditions for detoxification and make a comparison with Ca(OH)2 treatment feasible. As too harsh conditions lead to sugar degradation, the detoxification treatments were evaluated through the balanced ethanol yield, which takes both the ethanol production and the loss of fermentable sugars into account. The optimization treatments were performed as factorial experiments with 3-h duration and varying pH and temperature. Optimal conditions were found roughly in an area around pH 9.0/60 degrees C for NH4OH treatment and in a narrow area stretching from pH 9.0/80 degrees C to pH 12.0/30 degrees C for NaOH treatment. By optimizing treatment with NH4OH, NaOH, and Ca(OH)2, it was possible to find conditions that resulted in a fermentability that was equal or better than that of a reference fermentation of a synthetic sugar solution without inhibitors, regardless of the type of alkali used. The considerable difference in the amount of precipitate generated after treatment with different types of alkali appears critical for industrial implementation.

Development of acid stable, hyper-crosslinked, silica-based reversed-phase liquid chromatography supports for the separation of organic bases.

A new generation of extremely acid stable "hyper-crosslinked" (HC) phases have been developed with good plate counts for basic drug separations. In our previous work, we successfully developed an approach for synthesizing HC stationary phases on silica substrates using aluminum trichloride catalyzed Friedel-Crafts (F-C) chemistry to improve the stability of silica-based RPLC stationary phases at low pH. However, the performance of basic analytes on these HC phases under acidic conditions was unusually poor compared to that of conventional silica-based C18 phases. The effects of the specific F-C catalysts used and the specific silica substrate on the chromatographic properties of HC phases have been studied. Modified synthetic strategies that give both good observed plate counts for basic analytes under acidic conditions and very good low pH stability without compromising other chromatographic properties of the hyper-crosslinked phases have been developed. Replacement of aluminum trichloride with tin tetrachloride as the catalyst for the F-C chemistry and use of a very high purity silica result in significantly improved plate counts for basic analytes. In formic acid buffered mobile phases, which are highly compatible with electrospray ionization LC-MS, basic analytes showed much better performance on the tin tetrachloride catalyzed HC phases than on any conventional commercial phase tested. The tin tetrachloride catalyzed HC phase is as stable as the original aluminum trichloride catalyzed HC phases, and much more stable than the bench mark acid stable commercial phase.

Preparation and applications of weak acid cation exchanger based on monodisperse poly(ethylvinylbenzene-co-divinylbezene) beads.

New technology is reported here for the synthesis of an effective weak acid-cation exchanger for ion chromatography. Monodisperse macroporous poly(ethylvinylbenzene-co-divinylbezene) (PEVB-DVB) beads of 5 microm diameter were prepared by a two-step swelling and polymerization method. Then carboxyl groups were introduced by polymerization of maleic anhydride with unreacted vinyl groups on the resin beads, followed by hydrolysis of the maleic anhydride groups. A column packed with the carboxylate beads was used to separate alkali and alkaline earth metal ions in a single isocratic run. Separations were found to be better than those with similar resin particles that are simply coated with maleic acid. The columns containing the new particles were 100% compatible with solvents commonly used for HPLC. Additionally, the prepared column was stable and could be used for a long time in a wide range of pH. The column gave good resolution, low detection limits and good repeatability for the separation of common cations. Satisfactory results were also obtained for separations of organic amines and of common cations in rainwater.

Investigation on liquid chromatographic separation of basic compounds using silica column with aqueous/organic mobile phase containing triethylamine and acetic acid.

A high-performance liquid chromatography (HPLC) method using silica column eluted with aqueous solvent mobile phase containing triethylamine (TEA) and acetic acid (ACH) at trace percentages was characterized for the analysis of basic compounds. The key mechanism of this system is ion-exchange accompanying interaction of silanol groups. The increase in the ACH concentration in the mobile phase minimizes the ionization of the silanol group, leading to reduced retention time. However, the greater extent of ionization of silanol caused by the increase of TEA concentration helps to retain basic compounds in the column. Further, the protonated TEA that is positively charged also competes for the ionized silanol group with basic compounds, resulting in the modification of retention time. On the other hand, the retention becomes longer with increasing proportion of either organic or aqueous solvent in mobile phase, and partial replacement of methanol with acetonitrile.

Size-exclusion chromatography of biological samples which contain extremely alkaline proteins.

An improved size-exclusion chromatography (SEC) was developed to isolate extremely basic (alkaline) proteins, such as trypsin (pI=10.5), lysozyme (pI=11), and histone (pI=10.8). Develosil 300 Diol-5 (300 x 8 mm I.D., 30 nm average pore diameter) column was used with an eluent of 0.1 M sodium phosphate, 1.5 M sodium chloride, glycerol (40%, v/v), 2-propanol (10%, v/v), and Brij-58 (1%, v/v). Under these conditions, the final apparent pH becomes to 4.0, and pH adjustment is not necessary. Column temperature and flow rate were 15 degrees C and 0.2 ml/min, respectively. This elution system is stable and reliable, and applications onto human pancreatic juice, human bile, and tissue homogenates were successfully achieved. Since this system is convenient for protein analysis, it is expected to be generally applicable to clinical and biochemical research for identifying protein components in combination with microsequencing.

Retention of alkali, alkaline earth and transition metals on an itaconic acid cation-exchange column. Eluent pH, ionic strength and temperature effects upon selectivity.

The unusual selectivity of a methylene succinic (itaconic) acid modified polymeric column was investigated for the separation of alkali, alkaline earth, transition and heavy metals employing non-chelating inorganic eluents. The retention of selected metal ions on the column was investigated with simple HNO3 eluents and eluents prepared from KNO3 and KCl salts of varying pH (adjusted using HNO3). From these studies both the effect of eluent ionic strength and pH upon retention was evaluated for the itaconic acid stationary phase. The results obtained showed that despite slow exchange kinetics causing poor efficiencies, acceptable baseline separations of selected alkaline earth and transitions could be obtained under optimum conditions (the baseline separation of Mg(II), Ca(II), Mn(II), Cd(II), Zn(II) and Co(II) was possible using a 15 mM KNO3-5 mM KCl eluent at pH 3.50 in under 25 min). The use of an simple ionic strength step gradient was shown that facilitated the addition of Pb(II) to the above group of metal ions. An investigation into the effect of temperature upon peak efficiency and retention showed increased column temperature could be used to improve the resolution of closely eluting metal ions such as Ca(II) and Sr(II) and Ca(II) and Mn(II).

Organic modifiers for the separation of organic acids and bases by liquid chromatography.

A straight-chain alcohol or diol additive in the mobile phase was used to modify and improve the HPLC separation of organic acids and bases. Incorporation of 2% 1-butanol, 1% 1,2-hexanediol, or 0.25% 1,2-octanediol into an aqueous mobile phase greatly improved the separation of alkane carboxylic acids on a silica C18 column, both in terms of separation time and peak shape. When 1.5% 1-hexanol, 0.09% 1-decanol or 0.01% 1-dodecanol was added to an acetonitrile-water (30:70) mobile phase, much sharper peaks and better resolution were obtained for aromatic bases separated on an underivatized polystyrene-divinylbenzene column. The mobile phase additive is believed to coat the stationary phase surface by a dynamic equilibrium. The coated surface is more hydrophilic and facilitates the efficient partitioning of analytes between the mobile and stationary phases.

[Preparation of monodispersed agglomerated pellicular cation exchange resins and its chromatographic properties].

A new and simple method for the preparation of latex-coated pellicular cation exchanger is introduced. Chromatographic stationary phase of monodispersed agglomerated pellicular cation was prepared for the first time. The monodispersed polyvinylbenzene-divinylbenzene (PSTDVB) particles (10 microns) as substrate beads were functionalized with a tertiary amine on the surface at first and then attached with a layer of sulfonated latex particles (0.2 micron) to give the desired packing. Its chromatographic properties were evaluated by using alkali metals (Li+, Na+, NH4+, K+) and alkaline earth metals (Mg2+, Ca2+). The results showed that the packing is of good resolution, low detection limit, and excellent repeatability for common inorganic cations.