Inclusive separation of acetophenone from petrochemical by‐product with 1‐phenylethanol via noncovalent interactions

Separation of the barely studied mixture of acetophenone and 1‐phenylethanol, a typical by‐product obtained by oil refinery plant, based on the preferential affinity of β‐cyclodextrin (abbreviated as β‐CD) for acetophenone is focused. To demonstrate the potential application of β‐CD for separation of acetophenone from 1‐phenylethanol, the noncovalent interactions of β‐CD with acetophenone and 1‐phenylethanol were compared from thermodynamic and conformational points of view. For the purpose of separation, a multicomponent coprecipitation technique has been established based on the selective noncovalent binding property of β‐CD, which has been proved rigorously. Under the optimized conditions, the acetophenone/1‐phenylethanol equimolar binary mixture can be separated with a separation factor >37. For the petrochemical by‐product, which contains 74.93 wt % of acetophenone, 17.79 wt % of 1‐phenylethanol, and other minor compounds, expanding the separation scale, content of acetophenone in complex can get 99.2%, and the separation efficiency of β‐CD kept stable after recycling twice. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2962–2975, 2014     

Biocatalytic kinetic resolution of rac‐1‐phenylethanol and rac‐2‐pentanol in hexane medium: ACYL donor and water content effects

The kinetic resolutions of rac‐1‐phenylethanol and rac‐2‐pentanol by transesterification with vinyl esters catalysed by a commercial immobilised Candida antarctica lipase B were successfully carried out in hexane medium. This enzyme showed very high enantioselectivity for both substrates. The influence of the water content of the medium on the synthetic activity, selectivity and enantioselectivity of the enzyme was analysed, with the optimal amount of water about 100 ppm. Our results also showed that the activity per gram enzymatic derivate of CaLB was slightly higher with butyl butyrate as acyl donor.     

Enhancement of bioconversion gangliosides to monosialotetrahexosylganglioside by in situ sialic acid removal and recovery

Monosialotetrahexosylganglioside (GM1) production via bioconversion from gangliosides is promising for industrial application because it has the advantages of a high GM1 yield and an environmentally friendly process. Sialidase hydrolyzes gangliosides to GM1 producing sialic acid as a by‐product, which inhibits the sialidase activity, while the incomplete conversion of gangliosides was indicated by thin‐layer chromatography (TLC) in the presence of sialic acid. The sialic acid showed competitive inhibition on the sialidase activity with an inhibition constant of 0.75 mmol/L. By harnessing the in situ product removal (ISPR) technique, 50 g/L of crude gangliosides was completely converted to GM1 after a 12 h conversion. The GM1 concentration increased from 0.42 to 10.88 g/L in the ISPR system, which was 59.1 % higher than that of the control (6.84 g/L GM1). In addition, sialic acid was recovered simultaneously with a yield of 74.7 %. In summary, the ISPR system improved the bioconversion from gangliosides to GM1 and recovered sialic acid within a one‐step bioprocess.     

Productivity enhancement of S‐adenosylmethionine in Saccharomyces cerevisiae using n‐hexadecane as oxygen vector

BACKGROUND: Saccharomyces cerevisiae is one of the main microorganisms that can produce S‐adenosylmethionine (SAM) from L‐methionine and ATP with high productivity. To satisfy the ATP requirement for SAM synthesis, sufficient oxygen should be supplied to the medium to improve aerobic metabolism in S. cerevisiae. In this study, n‐hexadecane used as oxygen vector for enhancement of SAM production by this yeast was investigated. RESULTS: N‐hexadecane was most favorable for cell growth and SAM synthesis in S. cerevisiae when added at the time of inoculation. It could increase glucose consumption, reduce ethanol accumulation, and ultimately improve biomass and SAM productivity in a fermentation process. In a bioreactor, the highest yield of SAM (2.27 g L^?1) was achieved in the presence of 4% (v/v) n‐hexadecane after 24 h of inoculation, which was 23.37% higher than the control (1.84 g L^?1). CONCLUSION: The addition of n‐hexadecane to cultures of S. cerevisiae significantly enhanced SAM production without increasing energy consumption, and has the potential for use in large‐scale fermentation processes to increase oxygen supply. Copyright © 2012 Society of Chemical Industry     

酵母耦合原位分离技术不对称合成(R)-扁桃酸甲酯

以酿酒酵母(Saccharomyces cerevisiae AS2.1392)全细胞为催化剂不对称还原苯甲酰甲酸甲酯合成(R)-扁桃酸甲酯,该催化剂催化速度快、操作稳定性好。研究了底物和产物浓度对反应初速度的影响,建立了底物和产物抑制模型,并采取分批加入底物和添加树脂的方式解除底物和产物抑制。通过考察不同树脂对底物和产物的吸附量以及对生物还原反应的影响,筛选出了一种较适合的大孔吸附树脂NKA-Ⅱ。在优化的树脂加入量和加入模式下,当底物浓度为180mmol/L时,产物产率由35.0%提高到71.2%,对映体过量值(ee)保持在95%左右。     

In‐situ product removal to enhance the yield of biocatalytic reactions with competing equilibria: α‐glucosidase catalysed synthesis of disaccharides

Transglycosylations are an important class of enzyme‐catalysed reaction that occur in most living organisms and which are finding increasing application for the synthesis of therapeutic compounds. Compared with other bioconversion processes, however, they generally suffer from low product yields. This is due to the fact that in aqueous environments water is able to undergo a nucleophilic attack of the enzyme–substrate complex, increasing the rate of the competing hydrolysis reaction. The equilibrium yield of such reactions is consequently only around 10% (w/w). Here, the potential of applying in‐situ product removal (ISPR), with the boronate‐containing affinity resin Affi‐Gel® 601, to the α‐glucosidase mediated conversion of phenyl α‐D ‐glucoside to phenyl α‐maltoside has been examined. ISPR can increase the product yield from such kinetically‐controlled reactions by removing the product from the bulk aqueous phase as soon as it is formed. In this way the competing hydrolysis reaction can be prevented and conversions potentially driven to completion. Initial experiments revealed that the optimum pH of the α‐glucosidase reaction in water–acetonitrile mixtures was between 5.5 and 6.5, whereas the optimum pH for binding of the product to the Affi‐Gel® 601 resin was between 8.0 and 8.5. Despite having to compromise on both the optimal conditions for glucosidation and for binding, an increase in product yield of 25% (w/w) was still possible following the implementation of ISPR at pH 8 in an aqueous medium containing 50% (v/v) acetonitrile. Similar results were found with the β‐galactosidase catalysed synthesis of phenyl α‐galactobiose, indicating the potentially generic nature of the ISPR methodology. While these initial results are promising, they indicate the need for more highly selective resins for carbohydrate adsorption (with higher capacities) if further increases in product yield are to be obtained. © 2001 Society of Chemical Industry     

Polyacrylate‐core/TiO2‐shell nanocomposite particles prepared by in situ emulsion polymerization

We report the preparation of polyacrylate‐core/TiO₂‐shell nanocomposite particles through in situ emulsion polymerization in the presence of nano‐TiO₂ colloid obtained by the hydrolysis of titanium tetrachloride. The resultant colloidal system can be stable for months without any precipitation. In a typical sample, the diameter of nanocomposite particles was about 150 nm, and the thickness of TiO₂‐shell was 4–10 nm. Only cetyltrimethylammonium bromide was employed to provide the latex particles with positive charge, which was enough for the formation of fine TiO₂ coatings. Three initiators were tested. Ammonia persulfate was the most suitable one, because the cooperative effect was formed by the negatively charged TiO₂ particles and the terminal anionic group (SO₄^2?, the fraction of Ammonia persulfate) of the polymer chain on the surface of latex particles to maintain the stability of nanocomposite system. The pH value played a vital role in obtaining a tight TiO₂ coating. Transmission electron microscopy, X‐ray diffraction and Atomic force microscopy were used to characterize this nanocomposite material. It was found that rutile and anatase coexisted in the nanocomposite film. This may suggest a potential application in the field of photocatalytic coating. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1466–1470, 2006     

Encapsulation of diclofenac sodium with acidic copolymer hydrogels based on PEG/poly(N‐isopropylacrylamide‐co‐2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) semi‐interpenetrating network using in situ loading technique

A pH‐ and temperature‐responsive semi‐interpenetrating copolymer PEG6000/poly(NIPA‐co‐AMPS) (PEG/AMPS‐co‐NIPA SIPN), for short PEG SIPN, was made by ammonium persulfate‐initiated suspension copolymerization of N‐isopropylacrylamide, 2‐acrylamido‐2‐methylpropanesulphonic acid, and N,N′‐methylene‐bis‐acrylamide (MBAA; crosslinker) in the presence of PEG6000. The PEG SIPN copolymer matrices containing nanostructures made in the high‐temperature copolymerization resulted in channels for PEG and facile migration of drugs. In drug encapsulation or drug‐loading process, one can easily ignore or pay less attention to the interaction between a drug and its encapsulation materials; however, the ignored interactions may induce problems in drug properties or the release behavior in use. Sodium diclofenac (DFNa) precipitates as the carboxylic acid form in an acidic environment, and it is challenging to encapsulate sodium diclofenac in such an acidic matrix without precipitation of the sparingly soluble acid form of DFNa on the surface of the polymer substrate. To avoid bulky precipitation in drug loading, an in situ loading technique was developed for producing gel spheres with DFNa uniformly distributed in the polymer matrix. The technique is based on fast polymerization of spherical droplets of a pregel solution in which the drug is dissolved. Diffusion‐loading prodrugs were made in comparison with in situ loading prodrugs in thermal, release kinetics, and release behavior. Drug release profiles (in pH 7.4 phosphate buffer) show that the new drug loading technique gives controlled release during a period of about 7 days at 37°C. By contrast, gel spheres loaded with sodium diclofenac using the conventional diffusion technique produced almost total release of the drug within about 24 h. The thermal stability of sodium diclofenac, the PEG/AMPS‐co‐NIPA SIPN, and the prodrugs made with the SIPN and sodium diclofenac was studied. A near zero‐order release kinetics was found in the in vitro release of sodium diclofenac with in situ loading PEG SIPN prodrug. We have, for the first time, studied sodium diclofenac release behavior from the PEG SIPN hydrogel systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A Completely Biodegradable Poly[(L‐lactide)‐co‐(ε‐caprolactone)] Elastomer Reinforced by in situ Poly(glycolic acid) Fibrillation: Manufacturing and Shape‐Memory Effects

A new completely biodegradable shape‐memory elastomer consisting of PLLCA reinforced by in situ PGA fibrillation is described. The manufacturing processes and shape‐memory effects of the composites are discussed. DMA results reveal a strong interface interaction between in situ PGA fibrillation and PLLCA. Compared with the SMP‐based composites that are commonly used, the shape‐memory test shows that in situ PGA fibrillation can improve the recovery properties of PLLCA; in fact, the shape‐recovery rate increases from 80.5 to 93.2%.

     

Semi‐continuous enzymatic synthesis of cefaclor enhanced by in situ product removal

Enzymatic synthesis of cefaclor was carried out with kinetic control. The product yield was improved by the continuous removal of product from the reaction mixture via complexation of cefaclor with 1‐naphthol. The effects of pH and temperature on the enzymatic and complexing reactions were investigated. The efficiency of the enzymatic conversion of cefaclor in the complexing reaction was 80% under optimum reaction conditions. In situ product removal (ISPR) decreased product concentration in the bioreactor, consequently the yield of cefaclor increased from 57% (without ISPR) to 80% (with ISPR). The specially designed reactor allowed enzymatic reaction and product removal to be accomplished simultaneously, in which the productivity of cefaclor was improved to 65 g dm^?3 by semi‐continuous operation lasting for 55 h. Copyright © 2004 Society of Chemical Industry     

In situ entrapment of α‐chymotrypsin in the network of acrylamide and 2‐hydroxyethyl methacrylate copolymers

A mild and reproducible method has been developed for the entrapment of α‐chymotrypsin into a crosslinked copolymer. A porous copolymer was synthesized at 293 K by solution copolymerization of acrylamide and 2‐hydroxyethyl methacrylate. α‐Chymotrypsin was entrapped during copolymerization at different polymerization stages. The effect of crosslinking on enzyme loading and retention of its activity was examined. Copolymer with 2% crosslinking could entrap >90% of the enzyme. The activity of free and immobilized α‐chymotrypsin was determined by using N‐benzoyl‐L ‐tyrosine ethyl ester and casein as low and high molecular weight substrates respectively. Storage as well as thermal stability of the immobilized enzyme was superior to that of the free one. Effect of calcium and heavy metal ions was studied on immobilized enzyme activity. The immobilized enzyme showed little variation in activity with pH and retained 50% activity after nine cycles. The Michaelis constant K_m of the free and immobilized enzyme was estimated to be 2.7 and 4.2 × 10⁻³ mM, respectively, indicating no conformational changes during entrapment. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2996–3002, 2000     

Preparation the Key Intermediate of Angiotensin‐Converting Enzyme (ACE) Inhibitors: High Enantioselective Production of Ethyl (R)‐2‐Hydroxy‐4‐Phenylbutyrate with Candida boidinii CIOC21

Forty microorganisms belonging to different taxonomical groups were used to catalyze the enantioselective reduction of ethyl 2‐oxophenylbutyrate to afford the corresponding ethyl 2‐hydroxy‐4‐phenylbutyrate. Several microorganisms led to over 99% ee of ethyl (S)‐2‐hydroxy‐4‐phenylbutyrate. Especially, we firstly found that the Candida boidinii CIOC21 could be effectively used for the enantioselective preparation the ethyl (R)‐2‐hydroxy‐4‐phenylbutyrate in pure aqueous medium with 99% ee, a key intermediate in the production of angiotensin‐converting enzyme (ACE) inhibitors.     

Mechanistic insights into methanol‐to‐olefin reaction on an α‐Mn2O3 nanocrystal catalyst

The synthesis and utilization of an α‐Mn₂O₃ nanocrystal catalyst for methanol‐to‐olefin reaction is described. A methanol conversion of 35% and a maximum selectivity of 80% toward ethylene were obtained at 250^°C. In particular, formaldehyde, a primary intermediate for the reaction, was used to produce ethylene via a coupling reaction. A conversion of 45% and a selectivity of 66% to ethylene were achieved at 150^°C in a formaldehyde stream. In situ diffuse reflectance infrared Fourier transform spectra reveal the formation of the surface CH₂‐containing species during reaction, which implies that the main pathway for formaldehyde coupling is probably through interactions of those intermediates. In addition, the weakly adsorbed oxygen on the α‐Mn₂O₃ nanocrystal surface was found to play an important role in this reaction. © 2012 American Institute of Chemical Engineers AIChE J, 2012     

The influence of interphase on nylon‐6/nano‐SiO2 composite materials obtained from in situ polymerization

Three commercially available silane, titanate and aluminate based coupling agents were used to pretreat nano‐SiO₂ for the preparation of nylon‐6/nano–SiO₂ composites via in situ polymerization. The interphases formed in different composite systems and their influence on material properties were investigated. Results indicated that the interfacial interactions differed between composite systems, whereas rigidity and toughness of composites were all improved by addition of pretreated silicas at an optimal content of 4.3 wt%. The presence of pretreated silicas did not have a distinct influence in the non‐isothermal crystallization behaviour of the nylon matrix. The composites containing pretreated silicas had slightly higher dynamic viscosities and superior storage moduli at high frequency, compared with neat nylon‐6. Copyright © 2003 Society of Chemical Industry