Selective Separation of Cinnamic and p‐Methoxycinnamic Acids by Facilitated Pertraction

Abstract

Cinnamic acid can be selectively separated from p‐methoxycinnamic acid by facilitated pertraction with Amberlite LA‐2 dissolved in dichloromethane, using a U‐shaped pertraction cell which allows obtaining the free liquid membrane. The pertraction has been analyzed by means of initial and final mass flows, permeability and selectivity factors. The main factors which control the pertraction selectivity were identified to be the pH‐gradient between the feed and stripping phase and the mixing intensity of the aqueous phases. The maximum selectivity factor has been recorded for pH=2 of feed phase, pH=8 of stripping phase, rotation speed lower than 300 rpm, and carrier concentration higher than 40 g/l.     

Surfactant Synthesis via Lipase Esterification of Methyl α-d-Glucopyranoside with Selected Aliphatic Carboxylic Acids

Lipase‐catalyzed esterification and properties of synthesized carbohydrate esters were investigated. Methyl α‐d ‐glucopyranoside was the acyl group acceptor and different carbon atom chain lengths of aliphatic carboxylic acids (C12, C14 and C16) as the acyl group donors were applied in the esterification. Physico‐chemical studies on the synthesized carbohydrate esters were carried out. It was found that melting point for the methyl 6‐O‐hexadecanoyl‐α‐d ‐glucopyranoside was the highest consecutively followed by methyl 6‐O‐tetradecanoyl‐α‐d ‐glucopyranoside and methyl 6‐O‐dodecanoyl‐α‐d ‐glucopyranoside. Liquid crystal properties of the synthesized carbohydrate ester synthesized were evaluated via optical polarized microscopy. It was found that the liquid crystal textures for mono‐substituted carbohydrate esters were of the smectic phase. In a quaternary system (carbohydrate ester/n‐butanol/n‐hexadecane/water), a maximum 34 % of water (by mass) was contained in the monophasic region of methyl 6‐O‐tetradecanoyl‐α‐d ‐glucopyranoside and a maximum of 52 % water (by mass) was contained in a monophasic methyl 6‐O‐dodecanoyl‐α‐d ‐glucopyranoside. For methyl‐6‐O‐dodecanoyl‐α‐d ‐glucopyranoside, its concentration at aggregation was 5.2 × 10^?4 mM, with minimum air/water surface tension of 26 mN m^?1. The Gibbs energy of micellization was calculated at ?50 kJ mol^?1. The maximum adsorption density of methyl 6‐O‐dodecanoyl‐α‐d ‐glucopyranoside was determined at 4 × 10^?6 mol m^?2 while its minimum area per surfactant molecule at the air/water surface was 47 Ų.     

Characterization of the Suillus grevillei Quinone Synthetase GreA Supports a Nonribosomal Code for Aromatic α-Keto Acids

The gene greA was cloned from the genome of the basidiomycete Suillus grevillei. It encodes a monomodular natural product biosynthesis protein composed of three domains for adenylation, thiolation, and thioesterase and, hence, is reminiscent of a nonribosomal peptide synthetase (NRPS). GreA was biochemically characterized in vitro. It was identified as atromentin synthetase and therefore represents one of only a limited number of biochemically characterized NRPS-like enzymes which accept an aromatic α-keto acid. Specificity-conferring amino acid residues-collectively referred to as the nonribosomal code-were predicted for the primary sequence of the GreA adenylation domain and were an unprecedented combination for aromatic α-keto acids. Plausible support for this new code came from in silico simulation of the adenylation domain structure. According to the model, the predicted residues line the active site and, therefore, very likely contribute to substrate specificity.     

Ion-Exchange Preparative Chromatography of Amino Acids

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Zirconium and Hafnium Separation,Part 3. Ligand‐Enhanced Separation of Zirconium and Hafnium from Aqueous Solution using Nanofiltration

Abstract

Membrane filtration equipment was used to evaluate zirconium and hafnium separation efficiency by a membrane separation process. High rejection of Zr and Hf species in aqueous solution were obtained with nanofiltration and ultrafiltration membranes. This high rejection could be explained by the formation of high molecular weight polynuclear species. Enhanced transportation across the nanofiltration and ultrafiltration membranes was observed when aminocarboxylic ligands, like EDTA, were introduced in the solution. This enhancement could be explained by a depolymerization process of the polynuclear complexes induced by the ligands. The rejection of Zr and Hf was markedly influenced by the counter anions and the EDTA/metal ratio. By using Zr and Hf oxynitrates instead of oxychlorides a difference of rejection of up to 20% was observed for Zr and Hf indicating that the membrane separation process could be an alternative process for Zr and Hf separation.     

Separation of Quercentin by Pre-dispersed Solvent Extraction

Pre-dispersed solvent extraction (PDSE) was used to extract quercentin from its diluted solution. The influences of temperature, phase volume ratio (PVR), concentration of sodium Dodecyl benzene sulphonate and pH value etc. on the extraction efficiency were examined. It is found that, compared with traditional extraction techniques under the same condition, a higher extraction productivity can be obtained by PDSE. The stability of colloidal liquid aphrons plays an important role in this process. In a certain scope, the extraction efficiency increases with PVR. Excessive amount of solvent is not much helpful. A new analytical method by using ultraviolet spectrometer to determine the concentration of quercentin is established.     

Separation of Proteins by Electrophoretic Affinity Chromatography

A new kind of electrophoretic affinity chromatography (EAC) for bioseparation was proposed,Separation by EAC was conducted in a multicompartment electrolyzer in which the affinity gel media were packed in one of the central compartments.The presence of an electric field accelerated the migration of proteins inside the gel matrix during adsorption and descrption processes,This led to the increase of the overall speed of separation,The present study was focused on the effect of the strength of the electric field on adsorption and desorption processes.     

Fouling-resistant Composite Membranes for Separation of Oil-in-water Microemulsions

Fouling-resistant ceramic-supported polymer composite membranes were developed for removal of oil-in-water （O/W） mieroemulsions. The composite membranes were featured with an asymmetric three-layer structure, i.e., a porous ceramic membrane substrate, a polyvinylidene fluoride （PVDF） ultrafiltration sub-layer, and a polyamide/polyvinyl alcohol （PVA） composite thin top-layer. The PVDF polymer was east onto the tubular porous ceramic membranes with an immersion precipitation method, and the polyamide/PVA composite thin top-layer was fabricated with an inteffaeial polymerization method. The effects of the sub-layer composition and the recipe in the inteffaeial polymerization for fabricating the top-layer on the structure and performance of composite membranes were systematically investigated. The prepared composite membranes showed a good performance for treating the O/W microemulsions with a mean diameter of about 2.41μm. At the operating pressure of 0.4MPa, the hydraulic permeability remained steadily about 190L·m^-2·h^-1, the oil concentration in the permeate was less than 1.6mg·L^-1, and the oil rejection coefficient was always higher than 98.5% throughout the operation from the beginning.     

A Promiscuous Cytochrome P450 Hydroxylates Aliphatic and Aromatic C−H Bonds of Aromatic 2,5-Diketopiperazines

Cytochrome P450 enzymes generally functionalize inert C−H bonds, and thus, they are important biocatalysts for chemical synthesis. However, enzymes that catalyze both aliphatic and aromatic hydroxylation in the same biotransformation process have rarely been reported. A recent biochemical study demonstrated the P450 TxtC for the biosynthesis of herbicidal thaxtomins as the first example of this unique type of enzyme. Herein, the detailed characterization of substrate requirements and biocatalytic applications of TxtC are reported. The results reveal the importance of N-methylation of the thaxtomin diketopiperazine (DKP) core on enzyme reactions and demonstrate the tolerance of the enzyme to modifications on the indole and phenyl moieties of its substrates. Furthermore, hydroxylated, methylated, aromatic DKPs are synthesized through a biocatalytic route comprising TxtC and the promiscuous N-methyltransferase Amir_4628; thus providing a basis for the broad application of this unique P450.     

Prediction of the Elution Profile of Aromatic Compounds in RP‐HPLC

Abstract

An efficient prediction method for the elution profile was used to separate aromatic compounds such as benzene, toluene, chlorobenzene, o‐xylene, and 1,2‐dichlorobenzene by RP‐HPLC. The retention factor and bandwidth were predicted under linear‐gradient condition with the three retention models. The elution profiles were calculated based on the linear and quadratic equations of retention factor, lnk=lnk _w +S?, lnk=L+M?+N?², k=A+B/?, where ? was the vol.% of methanol. The elution profiles were calculated by the Gaussian distribution with obtained retention factor and bandwidth. Two kinds of experiments were performed; one is the isocratic runs to estimate the coefficients of three retention models, and the other is the linear gradient runs that were carried out with same initial mobile phase composition (water/methanol=96/4, vol.%), two final mobile phase compositions (water/methanol=24/76 and 40/60, vol.%), and three gradient times (20, 40, and 60 min). The predicted elution profiles by the three retention models and new prediction method have good agreement with experimental data in the employed gradient conditions. The minimum average errors of calculated and experimental results of aromatic compounds were lower than 3.5% by Bi‐poly equation.     

Compound Separation by Cyclic,Selective Dissolution. Isolation of Diastereomeric, 1β-Methylcarbapenem Key Intermediates

Abstract

A practical method for separation of the methyl esters of two diastereomeric, α-methylated, 2-azetidinon-4-ylacetic acid derivatives by selective dissolution using two solvents in which their relative solubilities are distinctly different is described. The less soluble diastereomer was first isolated from isopropanol in which the solubility of the more soluble diastereomer is 1.65 times that of the less soluble diastereomer. The more soluble diastereomer was then isolated from the mother liquor after a solvent switch to toluene in which the solubility of the more soluble diastereomer is only 1.15 times that of the less soluble diastereomer. The isolation cycle was then repeated to separate more of the diastereomers. This method is particularly useful for isolation of the more soluble component. A proposed explanation of the solubility differences suggests that the approach may be widely applicable to the separation of other structurally similar compounds.     

Festschrift in Honour of Prof. K.T.Yu(Yu Guocong)——60 Years' Contributions to Mass Transfer Separation Science and Engineering

In this special issue,23 papers are selected from over a hundred of domestic and foreign contributions to the 4th National Conference on Mass Transfer and Separation Engineering (NCMS2011), which will be held on 18th -21 st of November 2011 in Tianjin.Thi     

Phase Separation and Crystallization of Phosphate–Silicate Glass Cores of Preforms of Fiber Optics

The phase separation and the emergence of nanocrystalline inclusions in phosphate–silicate preforms for optical fibers activated with ytterbium, which are obtained by the powder sintering methods with the vibrational mixing of the melt and the addition of ytterbium-containing nanoparticles into preforms, are studied. Nanocrystals of YbPO₄, SiO₂, and YbP₃O₉ are formed in the preforms in the low-temperature areas of the powder sintering process when using either of the methods. It is concluded that the phosphates are crystallized as a result of the phase separation from the glass phase enriched with ytterbium.     

Effect of Pre‐Filtration on Selective Isolation of Tat Protein by Affinity Membrane Separation: Analysis of Flux,Separation Efficiency,and Processing Time

Abstract

The isolation and purification of Tat protein from bacterial lysate using avidin‐biotin interaction in microfiltration membranes have been reported in the literature. To increase the efficacy of the technique, improvements in flux, Tat separation efficiency, and processing time are essential. In the current research work a pre‐filtration step was introduced to remove unwanted high molecular weight proteins and other impurities from feed prior to affinity membrane separation. Significant enhancement in flux and separation efficiency of Tat was observed. Processing time was also reduced significantly. For example, with UF pretreatment step the total Tat recovery was around four times higher (with processing time 25% lower) than that observed with the untreated feed. The quality of purified Tat was analyzed by SDS‐PAGE, Western Blot, and biotin analysis. Flux behavior in affinity separation was described by model equations.     

Separation Science—A Vital Tool of the Chemical Engineer

Abstract

Separation attempts reach back into the earliest history of mankind. Motivated by necessity, man developed methods of separation which, although crude by our standards, represented ingenious progress. Thus, food and condiment preparation had much to do with the development of processes such as leaching, solvent extraction, crystallization, evaporation, and the like.     

Separation of Campesterol and β‐Sitosterol from a Sterol Mixture

Abstract

By solvent crystallization using diethyl ether as the solvent on sterol mixture, brassicasterol and stigmasterol that contains a side chain with double bond were separated from campesterol and β‐sitosterol with a saturated side chain. The total campesterol and β‐sitosterol content in the liquid phase was more than 97% with a recovery of 12%. Multistage crystallization using acetone as the solvent could increase the recovery of campesterol and β‐sitosterol to 30%. By employing zeolite selective adsorption on the campesterol and β‐sitosterol fraction, β‐sitosterol can be recovered in the liquid phase with a purity of 95.2% and a recovery of 3% (overall recovery 1%). After desorbing in ethanol, campesterol adsorbed on the zeolite can be recovered with a purity of 95.4% and a recovery of 3.7% (overall recovery 1.6%).     

Polymer-Analog Transformations of Polycaproamide—Polyglycidyl Dimethacrylate Graft Copolymers under the Effect of Aromatic Diamine

The kinetic and thermodynamic parameters of amination of PCA—PGMA graft copolymer with p-phenylenediamine (initial reaction rate, reaction order in chemically active groups, and effective activation energy were determined. The high efficacy of p-phenylenediamine in splitting of PGMA -oxide groups, almost at the level of diamines of aliphatic structure, was demonstrated.     

Iridium‐Catalyzed Annulation of Aromatic Imines with 1,3‐Dienes via Direct Functionalization of an Aromatic C?H Bond

The [3+2] annulation of N‐sulfonyl aromatic imines with 1,3‐dienes proceeded via a direct C H functionalization to give 1‐aminoindane derivatives in high yields with high regio‐ and stereoselectivities. The iridium complex coordinated with a substrate 1,3‐diene displayed high catalytic activity. The reaction proceeds via the direct formation of the aryliridium(I) species from the aromatic aldimine and an iridium(I) acetate species via a concerted metalation‐deprotonation pathway.

     

Separation of ethyl acetate–isooctane mixture by heteroazeotropic batch distillation

This paper studies the separation of an ethyl acetate–isooctane mixture by heterogeneous azeotropic distillation in a batch rectifying column. An initial list of 60 candidates was studied but only methanol and acetonitrile were obtained as potential heterogeneous entrainers. These entrainers form a low boiling heterogeneous azeotrope with isooctane. Experimental verification of the miscibility gap with isooctane was performed at 25 °C for each entrainer giving a smaller region for methanol than for acetonitrile. Feasibility of the heterogeneous azeotropic batch distillation was carried out experimentally in a laboratory batch distillation column having 44 theoretical equilibrium stages and using a high reflux ratio. Several distillate fractions were taken as a function of the temperature at the top of the column. For both methanol and acetonitrile, the main fraction was defined by the condensed vapor providing a liquid–liquid split of the isooctane/entrainer heteroazeotrope into the decanter. Ethyl acetate impurity was detected in both decanted phases, but in much lower amount when using acetonitrile as entrainer. The process with acetonitrile also resulted in a shorter operating time and higher purity and recovery yield of isooctane as the main distillate product. Pure ethyl acetate remained into the boiler at the end of each process.