Drowning-out crystallization of l-proline: Effect of anti-solvent composition and processing parameters on crystal size and shape

Crystallization of l-proline was investigated using a drowning-out method. Due to the high water and alcohol solubility of l-proline, the recovery of an l-proline product by precipitation using the drowning-out method required suitable anti-solvents selected from immiscibility and solubility studies. Through past experience, acetone and NMP were carefully chosen for analogy and solubility tests in pure anti-solvent. Although phase separation occurred in acetone, ultrasound was used to mix the two immiscible phases and generate fine emulsion droplets. l-proline crystals were obtained using NMP with a general drowning-out method. A spherical agglomerate of l-proline was also obtained using acetone by emulsion solvent diffusion methods. The ultrasound power controlled the agglomerate sizes, and the agglomerate surface transformed from amorphous to crystalline as the residence time increased. Alternatively, when NMP was used as an anti-solvent, l-proline monocrystals with needle type morphology were produced.     

Application and Comparison of High-Speed Countercurrent Chromatography and High Performance Liquid Chromatography in Preparative Enantioseparation of α-Substitution Mandelic Acids

This paper is mainly about extending research on application and comparison of preparative high-speed countercurrent chromatography (HSCCC) and preparative high performance liquid chromatography (HPLC) in chiral separations. Preparative enantioseparations of α-cyclopentylmandelic acid and α-methylmandelic acid by HSCCC and HPLC were compared using hydroxypropy-β-cyclodextrin (HP-β-CD) and sulfobutyl ether-β-cyclodextrin (SBE-β-CD) as the chiral mobile phase additives. In preparative HPLC the enantioseparation was achieved on the ODS C₁₈ reverse phase column with the mobile phase composed of a mixture of acetonitrile and 0.10 mol L^?1 phosphate buffer at pH 2.68 containing 20 mmol L^?1 HP-β-CD for α-cyclopentylmandelic acid and 20 mmol L^?1 SBE-β-CD for α-methylmandelic acid. The maximum sample size for α-cyclopentylmandelic acid and α-methylmandelic acid was only about 10 mg and 5 mg, respectively. In preparative HSCCC the enantioseparations of these two racemates were performed with the two-phase solvent system composed of n-hexane-methyl tert.-butyl ether-0.1 molL^?1 phosphate buffer solution at pH 2.67 containing 0.1 mol L^?1 HP-β-CD for α-cyclopentylmandelic acid (8.5:1.5:10, v/v/v) and 0.1 mol L^?1 SBE-β-CD for α-methylmandelic acid (3:7:10, v/v/v). Under the optimum separation conditions, totally 250 mg of racemic α-cyclopentylmandelic acid could be completely enantioseparated by HSCCC with HP-β-CD as a chiral mobile phase additive in a single run, yielding 114-116 mg of enantiomers with 98-99% purity and 89-92% recovery. But, no complete enantioseparation of α-methylmandelic acid was achieved by preparative HSCCC with either of the chiral selectors due to their limited enantioselectivity. In this paper, preparative enantioseparation by HSCCC and HPLC was compared from various aspects.     

Mathematical modelling of the solubility of supercritical CO2 in poly(l-lactide) and poly(d,l-lactide-co-glycolide)

Two mathematical models, Sanchez–Lacombe equation of state and the Perturbed-Chain Statistical Associating Fluid Theory were applied for modelling the phase equilibrium for the poly(l-lactide)–CO₂ and poly(d,l-lactide-co-glycolide)–CO₂ systems. Aspen Polymer Plus software was used. The results were compared with previously obtained experimental values for solubility. The solubility of scCO₂ in the two biodegradable polymers was calculated for three different temperatures (308, 313 and 323 K) in the pressure range (10–30 MPa). The characteristic parameters for the components and the binary interaction parameters for the models were optimized in order to obtain the best fit between the estimated and the experimental gas solubility data. The results suggest that both SL EOS and PC-SAFT are reliable models in describing the phase equilibrium of the PLLA–CO₂ and PLGA–CO₂ systems at the proposed working conditions.     

Novel stereo controlled glycosylation of 1,2,3,4,6-penta-o-acetyl-β-d-glucopyranoside using MgO–ZrO2 as an environmentally benign catalyst

Glycosylation reactions are most commonly encountered in nature. Synthetically, glycosylations are carried out with Lewis acid catalysts or mineral acids. However an environmental threat associated with catalysts has encouraged process modification by alternative development of solid catalysts based glycosylation reactions, which are commercially viable as well. In this contribution comparative study of glycosidic bond formation of 1,2,3,4,6-penta-o-acetyl-β-d-glucopyranoside with various alcohols over variety of reaction promoters/catalyst like p-toluene sulphonic acid, HCl, H₂SO₄ and MgO–ZrO₂ were taken up to evaluate the performance of this potential promoter/catalysts systems. The best catalyst for the selective synthesis of alkyl-β-d-glucopyranosides was MgO–ZrO₂ which remains active upto three runs. This replacement of homogeneous acid catalysts by heterogeneous base catalyst shows alkyl-β-d-glucopyranoside as major product at comparatively low temperature range. The effects of variety of parameters were studied in a batch reactor. The mechanism of the reaction over basic mixed metal oxide at 363 K is put forth.     

Tailor-made gold brush nanoelectrode ensembles modified with l-cysteine for the detection of daunorubicine

A new functionalized l-cysteine surface modified 3D gold brush nanoelectrode assembly BNEE (l-cys/BNEEs) was prepared. The BNEEs consisted of gold nanowires 100 nm in diameter and up to 400 nm in length fabricated by template synthesis in track etched polycarbonate membranes. The nanowires were exposed by controlled chemical etching of the membrane and were then modified by coating l-cys on the surface of the exposed gold nanowires. The morphology of the BNEEs was imaged by scanning electron microscopy and the real active area of BNEEs was determined by electrochemical impedance spectroscopy. The redox of daunorubicine (DNR) at the l-cys/BNEEs exhibited absorption-controlled characteristics and higher current activity than that at l-cys surface modified 2D disk NEEs (l-cys/DNEEs). The square wave voltammetry technique was employed to detect DNR. The detection limit was 1.0 × 10⁻⁸ M (s/n = 3). The linear detection concentration range of DNR was from 2.5 × 10⁻⁸ to 4.0 × 10⁻⁷ M.     

Studies on the oxidation reaction of l-cysteine in a confined matrix of layered double hydroxides

The amino acid l-cysteine (l-Cys) was intercalated into a MgAl layered double hydroxide (LDH), and its oxidation reaction by hexacyanoferrate (III) (Fe(CN)₆³⁻) in the confined region between sheets of LDH has been studied in detail. Based on the measurement results of XRD, Raman and FT-IR, it was found that the interlayer l-Cys was oxidized to cystine by Fe(CN)₆³⁻. Furthermore, the kinetics of this reaction was investigated in batch mode. The influences of initial Fe(CN)₆³⁻concentration, l-Cys-LDH quantity and reaction temperature on the interlayer oxidation reaction have been studied, respectively. The reaction follows a diffusion-controlled mechanism represented by Crank-Ginstling and Brounshtein kinetic model with the apparent activation energy of 29.93 kJ/mol. Therefore, this layered material may have prospective application as a novel “molecular reactor” for confined chemical reactions.     

Refolding of recombinant N-acetyl-d-glucosamine 2-epimerase by a fed-batch process

N-Acetyl-d-glucosamine 2-epimerase is one of the key enzymes for the enzymatic synthesis of N-acetylneuraminic acid, a sialic acid and a critical precursor for the synthesis of some antiviral agents. Overexpression of the recombinant epimerase in Escherichia coli led to the formation of protein inclusion bodies. Refolding of guanidine HCl-solubilized protein by direct dilution resulted in the formation of soluble oligomers, mediated probably by hydrophobic interactions. The extent of aggregation of protein subunits into inactive oligomers could be efficiently reduced by employing fed-batch refolding process, in which the solubilized proteins were added continuously at a pre-determined rate. The yields of soluble proteins decreased with the feeding rates. The addition of glutathione into refolding buffer at certain stage of the refolding process could enhance the yield of soluble proteins more than two-fold, possibly by resolving the inadvertently formed disulfide bridges among the protein subunits that contain 10 cysteine residues each. Folding aids such as l-arginine and glycerol were found effective in increasing the yield of soluble proteins and the specific activity of the refolded proteins. Under the optimal condition, a specific activity of 0.47 IU/mg was obtained with an activity recovery yield of ca. 30%. The specific activity of the refolded proteins was significantly lower than that of the native protein, 1.23 IU/mg, indicating that more information concerning the 3D structure of native N-acetyl-d-glucosamine 2-epimerase and the role of its cofactor, ATP, for catalytic activity is needed for the development of a more efficient refolding process.     

Substantially enhancing enzymatic regioselective acylation of 1-β-d-arabinofuranosylcytosine with vinyl caprylate by using a co-solvent mixture of hexane and pyridine

Novozym 435-catalyzed regioselective acylation of 1-β-d-arabinofuranosylcytosine (ara-C) with vinyl caprylate for the preparation of its 5′-O-acyl derivative has been performed in six co-solvent mixtures and three pure polar solvents for the first time. Novozym 435 displayed low activity towards 1-β-d-arabinofuranosylcytosine in pure polar solvents, although those solvents can dissolve the nucleosides well. When a hexane–pyridine co-solvent system was adopted, both the initial rate and the substrate conversion were enhanced markedly. The most suitable co-solvent, initial water activity, reaction temperature and the molar ratio of vinyl caprylate to ara-C were hexane/pyridine (28/72, v/v), 0.03, 40 °C and 15, respectively. Under these conditions, the initial rate, the substrate conversion and the regioselectivity were as high as 99.0 mmol h⁻¹, 98% and >99%, respectively. The product of the Novozym 435-catalyzed reaction was characterized by ¹³C NMR and confirmed to be 5′-O-octanoyl 1-β-d-arabinofuranosylcytosine.     

Emulsion liquid membrane pertraction of L-lysine from dilute aqueous solutions by D2EHPA mobile carrier

The results of experimental studies on the batch extraction of L-lysine by emulsion liquid membrane are discussed and the capabilities of this method in the separation of solute from dilute aqueous solutions are shown. Studies on the extraction equilibrium for organic and aqueous phases were performed. The experimental results showed that the degree of extraction was increased by an increase in the pH of the feed phase, the concentration of [H⁺] in the internal phase, and concentration of the carrier in the organic phase. An optimum value of stirring speed was achieved. The rate of water swelling as an undesirable phenomenon was also measured.     

Synthesis of -leucine nanoparticles via physical vapor deposition at varying saturation conditions

Preparation of L-leucine nanoparticles by a process based on physical vapor deposition has been presented. In an aerosol flow reactor method, aqueous L-leucine droplets were first dried followed by the sublimation of L-leucine to produce vapor that upon vapor deposition resulted in L-leucine nanoparticles with size ranging from 40 to 200 nm. Onset temperature for the sublimation of L-leucine at concentrations from 0.02 to increased from 135 to , respectively. The formation of nanoparticles was initiated in three different ways: (i) via droplet drying, (ii) via heterogeneous nucleation of L-leucine vapor on solid L-leucine particles, and (iii) via homogeneous nucleation of L-leucine vapor to form new-born nanoparticles. Consequently, the saturation conditions of L-leucine vapor in the reactor determined the resulting particle size, size distribution and number concentration, those depending very much on nucleation mode. In general, the both nucleation modes produced narrow size distributions, that is, geometric standard deviation (GSD) was <1.8 although the number concentration increased with the increased amount of L-leucine vapor. Upon desublimation and vapor deposition, L-leucine formed leafy crystals whose size was the largest when produced from the heated section at the vicinity of the onset temperature and the smallest far above the onset temperature. All the particles prepared in the conditions (i)–(iii) were crystalline. However, X-ray diffraction analysis showed preferential direction for crystal growth according to the way of particle formation.     

Acid- and base-catalyzed hydrolyses of aliphatic polycarbonates and polyesters

Poly(propylene carbonate) (PPC) was synthesized by the zinc glutarate catalyzed copolymerization of carbon dioxide and propylene oxide (PO). Hydrolytic degradability of the PPC polymer was examined in tetrahydrofuran solutions containing 10 wt.% acidic or basic aqueous solutions of varying pH using viscometry and GPC analysis. Further, the hydrolysis behaviors of all PPC solutions were compared with those of poly(-caprolactone) (PCL) and poly(d,l-lactic acid) (PLA). All polymers studied show higher degradability in strong basic conditions than in strong acidic conditions, but very low degradability in moderate acidic, basic and neutral conditions. Moreover, PPC is degraded less in strong acidic conditions than the polyesters, while in strong basic conditions, the polycarbonate is more easily degraded. The difference in degradabilities of these polymers in acidic conditions is associated with the different nucleophilicities of their carbonyl oxygen atoms, while in basic conditions the differences are associated with the different electrophilicities of the corresponding carbonyl carbon atoms. With regard to the hydrolysis results and the structural and chemical nature of the polymer backbones, degradation mechanisms are proposed for the acid- and base-catalyzed hydrolyses of PPC, PCL and PLA.     

Dehydration of d-glucose in high temperature water at pressures up to 80 MPa

Reaction of d-glucose in water to yield 5-hydroxymethylfurfural (5-HMF), 1,2,4-benzenetriol (BTO) and furfural was studied at high temperatures (up to 400 °C) and high pressures (up to 80 MPa) using a continuous flow reactor. Maximum temperature and pressure conditions gave maximum furfural yield. Increasing pressure from 40 to 70 and 80 MPa enhanced dehydration reactions to 5-HMF, but also enhanced hydrolysis of 5-HMF leading to the production of BTO and thus lead to lower yields of 5-HMF (below 10%). Remarkably, the dehydration reaction to 5-HMF and the hydrolysis of 5-HMF were both enhanced by the increase in water density at 400 °C.     

Modification of glassy carbon electrodes by 4-chloromethylphenyl units and d-glucosaminic acid

The present work is dealing with the attachment of d-glucosaminic acid (D-GA) on glassy carbon electrode by two different methods. Firstly, the electrode was modified by chloromethylphenyl groups by reduction of 4-chloromethylphenyldiazonium cations followed by the nucleophilic substitution of the chlorine by the amine functionality of D-GA and secondly by the direct immobilization of the amine terminated molecule. The generality of the nucleophilic substitution reaction and the direct immobilization of an amine were also demonstrated with reactants bearing an electroactive ferrocene moiety; 4-nitrophenylferrocene (NFc) and 4-ferrocenylaniline (FcA). The surfaces modified with FcA and NFc were investigated by cyclic voltammetry, and the D-GA modified electrodes were characterized by X-ray photoelectron spectroscopy. A preliminary evaluation of the efficiency of these surface modifiers to prevent protein adsorption was realized by scanning electron microscopy.     

Synthesis of hectorite–TiO2 and kaolinite–TiO2 nanocomposites with photocatalytic activity for the degradation of model air pollutants

We studied the synthesis and photocatalytic activity of small-sized TiO₂ supported on hectorite and kaolinite. Deposition of TiO₂ on the clay mineral surface was conducted by using a sol–gel method with titanium isopropoxide as precursor. Anatase TiO₂ particles formation was achieved by hydrothermal treatment at 180 °C. Material characterization was conducted using XRD, SEM, XPS, ICP-OES, BET and porosimetry analysis. fficiency in synthesizing clay–TiO₂ composites depended strongly on the clay mineral structure. Incorporation of anatase in hectorite, an expandable clay mineral, was found to be very significant (> 36 wt.% Ti) and to be followed by important structural changes at the clay mineral surface. Instead, no major structural modifications of the clay were observed for kaolinite–TiO₂, as compared with the untreated material. Photocatalytic performance of clay–TiO₂ composites was evaluated with ATR-FTIR following the oxidation of adsorbed toluene and d-limonene, two model air pollutants. In either case, the photocatalytic removal efficiency of these hydrophobic substrates by the synthesized clay–TiO₂ composites was comparable to that observed using pure commercial TiO₂ (Degussa P25).     

An Interesting Complex: [Cd(l -trp) (d-trp)] n

A novel coordination polymer [Cd(l-trp) (d-trp)] _n (where l-trp and d-trp are l-tryptophan and d-tryptophan or (S)-2-amino-3-(3-indolyl)propionic acid and (R)-2-amino-3-(3-indolyl)propionic acid) was prepared by a solvent-thermal method and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The compound(monoclinic space group P2(1)/c with a = 19.759(2) Å, b = 5.2496(10) Å, c = 9.7594(16) Å, β = 97.2760(10)°, Z = 2) shows a two-dimensional plane structure. The crystallized coordination polymer has a centrosymmetric space group. Each Cd²⁺ ion coordinates with a pair of racemes, and the complex is a mesomer. Although l-trp was used, both l-trp and d-trp appear in the complex.     

Hydroxyapatite/poly(L-lactic acid)-chitosan Porous Scaffolds Prepared by Phase Separation Method

Hydroxyapatite/poly(L-lactic acid)–chitosan and poly(L-lactic acid)/chitosan porous scaffolds were prepared by phase separation technique using heated acetic acid–water as a common solvent of poly(L-lactic acid) and chitosan. The results show that the distribution of hydroxyapatite in the scaffolds is good. The porosity of the hydroxyapatite/poly(L-lactic acid)–chitosan scaffolds is nearly 85%. The hydroxyapatite particles in the scaffolds are beneficial for improving the compression property of the scaffolds. The in vitro bioactivity test shows that there is a low crystallinity of carbonate hydroxyapatite coating formed on the surface of the scaffold after immersing in simulated body fluid for 14 days, indicating that the hydroxyapatite/poly(L-lactic acid)–chitosan scaffolds have a good bioactivity.     

Effect of d-isomer concentration on the coloration properties of poly(lactic acid)

Poly(lactic acid) (PLA) fibre is derived from annually renewable crops, it is 100% compostable and its life cycle potentially reduces the earth's carbon dioxide level. In this work PLA fabrics containing variable concentrations of the d- and l-isomers have been studied to ascertain their dyeability, the characteristics of those dyed polymers, and their subsequent performance and properties. Comparison of poly(lactic acid) fabrics with varying d-isomer content revealed differences in melting temperature; by virtue of a higher d-isomer concentration, ‘high d-’ fibres have greater fibre entropy which causes a decrease in melting temperature. As a result of greater fibre entropy, high d- fibres have more amorphous and less crystalline regions in the polymer, with respect to low d- fibres, hence, high d- fabrics display greater dye exhaustion and colour strength in comparison with their low d- counterpart in all dyes and all concentrations. In application of a dye mixture for a black shade, high d- fibres are able to be dyed to an excellent black shade, whereas low d- fibres appear very brown, due to lower exhaustion of the blue component of the mix. In terms of wash fastness, there is very little difference between high d- fibres and low d- fibres; this is because the glass transition temperature for both fibres is very similar.     

Suppression of β-crystal in iPP/PET Fiber Composites

The β-crystal formed in PP/PET fiber composites was investigated. The results indicate that PET fibers (PF) can preferably lead to α-crystal formation on their surface. Besides, α-crystals occur earlier than those in the bulk. The β-crystal, might be induced by temperature gradient, only formed away from the PF in composites with lower content of PF. The higher the content of PF is, more possible the PF network is constructed. The transcrystallinity induced by PF will rapidly occupy the region between the adjacent PFs. Consequently, owing to the spatial confinement, β-form is suppressed in the composites with higher content of PF.     

Preparation and characterization of carvedilol-loaded poly(d,l) lactide nanoparticles/microparticles as a sustained-release system

Carvedilol poly(d,l)-lactide nanoparticles/microparticles were prepared. The size and morphology of the developed particles were optimized to study the carvedilol release profile by studying the effect of organic solvents and polymer amount through atomic force microscopy analysis. Spherical particles were obtained with a minimum size of 125?nm in the case of acetone and a maximum size of 970?nm in the case of dichloromethane affording microparticles formation. The interaction was confirmed by differential scanning calorimeter and Fourier transform infrared. The in vitro release profile of the multicompartment system (pure carvedilol, loaded nanoparticles and microparticles) has shown a sustained release with Korsmeyer–Peppas with T lag model.     

Toughening Behavior of Poly(L-Lactic Acid)/Poly(D-Lactic Acid) Asymmetric Blends

The L-configured poly(lactic acid) has exhibited vast appeal in the past decades. However, most previous researches reveal that L-configured poly(lactic acid) exhibits fragile behavior, which limits its applications. Present work clarified that the toughness of poly(lactic acid) depended on the content of crystallites and rigid component incorporated into the specimens. The elongation at break was remarkably high in the L-configured poly(lactic acid)/D-configured poly(lactic acid) with a small amount of D-configured poly(lactic acid) (≤15%). The stretching led to orientation of crystals and amorphous molecular chains and segments. The crystals did not vary, while the amorphous molecular chains transited to mesophase during stretching, and this mesophase formed homocrystallites during heating.