A highly active and selective β‐nucleating agent for isotactic polypropylene and crystallization behavior of β‐nucleated isotactic polypropylene under rapid cooling

Zinc adipate (Adi‐Zn) was observed to be a highly active and selective β‐nucleating agent for isotactic polypropylene (iPP). The effects of Adi‐Zn on the mechanical properties and the β‐crystals content of nucleated iPP were investigated. The impact strength of iPP nucleated with 0.2 wt % Adi‐Zn was 1.8 times higher than that of neat iPP. In addition, wide‐angle X‐ray diffraction analysis indicated that the content of β‐crystals in nucleated iPP (k_β value) reached 0.973 with 0.1 wt % Adi‐Zn, indicating that Adi‐Zn is a highly active and selective β‐nucleating agent for iPP. Furthermore, fast scanning chip calorimetry (FSC) studies using cooling rates from 60 to 13,800 °C min^?1 revealed that the formation of β‐crystals significantly depended on the cooling rates. At cooling rates below 3000 °C min^?1, only β‐crystals existed. However, at cooling rates above 6000 °C min^?1, β‐crystals failed to form. Moreover, a lower critical crystallization temperature that corresponded to the generation of β‐crystals was investigated using cooling‐induced crystallization, and the results are in good agreement with those of a previous study. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43767.     

Effect of syndiotactic polystyrene on the crystallization behavior of isotactic polypropylene/syndiotactic polystyrene blends with and without β‐nucleating agent

Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min^?1) or low (2 °C min^?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals.     

Thermal and structural properties of sn-1,3-dipalmitoyl-2-oleoylglycerol and sn-1,3-dioleoyl-2-palmitoylglycerol binary mixtures examined with synchrotron radiation X-ray diffraction

Thermodynamic and polymorphic behavior of POP (sn-1,3-dipalmitoyl-2-oleoylglycerol) and OPO (sn-1,3-dioleoyl-2-palmitoylglycerol) binary mixtures was examined using differential scanning calorimetry and conventional and synchrotron radiation X-ray diffraction. A molecular compound, β_C, was formed at the 1:1 (w/w) concentration ratio of POP and OPO, giving rise to two monotectic phases of POP/compound and compound/OPO in juxtaposition. β_C has a long-spacing value of 4.2 nm with a double chainlength structure and the melting point of 31.9°C. A structural model of the POP-OPO compound is proposed, involving the separation of palmitoyl and oleoyl chain leaflets in the double chainlength structure. In the polymorphic occurrence of the POP-OPO mixtures, the POP fraction transformed from α to β′ with no passage through γ, then transformed to β. The presence of OPO in POP promoted the β′-β transformation of POP during the melt-mediated crystallization.     

Crystallization behavior of 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol and 1‐palmitoyl‐2,3‐dioleoyl‐glycerol

A model margarine was stored under a temperature fluctuation cycle of 5—20 °C until granular crystals were observed. Using information obtained from the granular crystals, the crystallization behaviors of major triacylglycerols of palm oil, 1,3‐dipalmitoyl‐2‐oleoyl‐glycerol (POP), 1‐palmitoyl‐2,3‐dioleoyl‐glycerol (POO), and their mixtures were then investigated. It was shown that in the model margarine, the POP content in the granular crystals was higher than in their surrounding materials, and the X‐ray diffraction pattern of the granular crystals revealed that they were the most stable polymorph, β. 99% pure POP, POO, and their mixtures were then stored under the above‐mentioned temperature cycle. POP was found to form the unstable polymorph, α, when cooled rapidly from the melt. Within 24 hours transformation into the γ polymorph and then into the β polymorph was observed. POO was shown to transform into the β' polymorph from α. When POP and POO were mixed, the β polymorph did not emerge, instead it was shown that POP and POO were both agglomerated in the mixtures, giving rise to the formation of granular crystals.     

Studies on the Non‐isothermal Crystallization Behavior of Aluminum Nanopowder‐Filled Poly(3,3‐bis‐azidomethyl Oxetane)

Non‐isothermal crystallization of aluminum nanopowder‐filled poly(3,3‐bis‐azidomethyl oxetane) (PBAMO) from melt at various constant cooling rates from 1 to 10 °C min⁻¹ was studied. Ozawa's approach was used to analyze non‐isothermal crystallization kinetics. It was found that Ozawa's approach was effective at medium constant cooling rate. The crystallization activation energy derived from Kissinger's equation was 80.8 kJ mol⁻¹. The experimental results showed that the aluminum nanopowder acted as a nucleating agent to raise the peak crystallization temperature and to accelerate the crystallization rate at higher constant cooling rates. Uniform crystals which showed one melting peak could be obtained at a constant cooling rate of 1 °C min⁻¹.     

A novel β‐nucleating agent for isotactic polypropylene

The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min^–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry     

Shear‐induced β‐form polypropylene in long chain branching isotactic polypropylene

Long chain branching polypropylene (LCBPP) with different long chain branching (LCB) contents were prepared by reactive extrusion in the presence of styrene and benzoyl peroxide, and their shear‐induced crystallization behaviors were investigated. The results indicated that the LCB structure extended the relaxation time of LCBPP in the molten state, which led to the formation of β‐form polypropylene under shear and high cooling rate. The content of β‐form (K_β) increased with the increase of LCB content, shearing rate and cooling rate. The K_β value of LCBPP3 whose weight average molecular weight was 920,000 g mol^?1 could be up to 52.0% with a shear rate of 60 s^?1 associated with a cooling rate of 280°C min^?1. This study is expected not only to have a deeper understanding of the shear‐induced crystallization behavior of LCBPP, but also provide a new strategy to obtain high level β‐form polypropylene. POLYM. ENG. SCI., 56:240–247, 2016. © 2015 Society of Plastics Engineers     

Mixing Phase Behavior of 1,3-Dipalmitoyl-2-Oleoyl-sn-Glycerol (POP) and 1,2-Dipalmitoyl-3-Oleoyl-rac-Glycerol (PPO) in n-Dodecane Solution

We examined the mixing phase behavior of 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) in organic solutions containing n-dodecane (C₁₂) as a solvent to confirm whether the molecular compound (MC) crystals of POP/PPO are formed as metastable and most stable forms in the dilute solution by using DSC and synchrotron radiation X-ray diffraction. The POP/PPO mixtures were prepared at different concentration ratios of POP and PPO with a 10 % increment in two solutions having weight concentration ratios of (POP+PPO):C₁₂ of 50:50 (50 % solution) and 20:80 (20 % solution). We found that MC crystals formed at a ratio of POP/PPO = 50/50 having the melting point of 23.1 and 20.6 °C in 50 and 20 % solution systems in stable states of incubated samples, respectively. The metastable (β′) and stable (β) forms of MC of POP/PPO = 50/50 having a double-chain-length structure were confirmed in kinetic behavior and thermodynamically stable states attained after long time incubation, in contrast to the triple-chain-length structure of stable forms of POP (β) and PPO (β′). In addition, we observed the formation of MC crystals of POP/PPO in diluted solutions having n-dodecane concentrations up to 98 % and conclude that molecular interactions between POP and PPO molecules to form MC crystals are not altered by solvent molecules in diluted solutions.     

Binary Phase Behavior of 1,3-Dipalmitoyl-2-oleoyl-<Emphasis Type="Italic">sn</Emphasis>-glycerol and 1,2-Dioleoyl-3-palmitoyl-<Emphasis Type="Italic">rac</Emphasis>-glycerol

1,3-Dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP) are two major molecular species that account for roughly half of the total triacylglycerols in palm oil. The binary phase behavior of a POP/OOP mixture plays an important role in the crystallization of palm oil. We conducted thermodynamic and kinetic studies of OOP and its mixtures with POP using differential scanning calorimetry and X-ray diffraction with a conventional generator and synchrotron radiation. We found that OOP has two polymorphs, α as a metastable form and β′ as the most stable form, and that the two forms are stacked in a triple-chain-length structure. The POP/OOP mixtures exhibited immiscible eutectic natures in both their metastable and their most stable states, in contrast to POP/1,2-dipalmitoyl-3-oleoyl-rac-glycerol and POP/1,3-dioleoyl-2-palmitoyl-sn-glycerol mixtures, in which molecular compounds of a double-chain-length structure were formed. A time-resolved synchrotron radiation X-ray diffraction study undertaken during the cooling and heating processes indicated that the α and β′ forms of the POP and OOP fractions crystallized and melted in separate manners, and that crystallization of the β′ form and the polymorphic transformation from α to β′ of POP and OOP are promoted in the presence of another component. The absence of molecular compound crystals in the binary mixtures of POP/OOP is explained by taking into account the molecular interactions of acyl chain packing, glycerol conformation, and methyl end stacking, among which glycerol conformation appeared to be most influential.     

Tripalmitin-Driven Crystallization of Palm Oil: The Role of Shear and Dispersed Particles

While palm oil (PO) is a reliable ingredient in formulations for biscuits, cream fillings, and compound chocolates, our understanding of its crystallization behavior and physico-chemistry pales in comparison to many other fats and oils. Phase diagrams of triacylglycerol (TAG) mixtures may be used to elucidate fat crystal polymorphism and composition of such oils, yet conditions important to the food industry such as shear speed, relevant processing temperatures, and presence of secondary ingredients are regularly overlooked. Here, the effects of shear speed (n = 0–500 RPM), dispersion concentration (0–5 wt.%), and dispersed particle surface chemistry [silica or octadecyl-functionalized (C18) silica] on the thermal properties of commercial PO when cooled from 60 to 20 °C at 1 °C min⁻¹ were explored, with focus placed on PO's higher-melting fraction. Using a series of high-purity TAG standards, X-ray diffraction revealed PO's higher-melting fraction as mainly composed of tripalmitin (PPP) crystals and molecular compounds (MC) of PPP either with 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) or with POP and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) in combination, all in a double chain-length β' (i.e., β'-2) conformation. Shear increased the formation of lower-melting α-2 POP and β'-2 MC_POP:PPO:PPP crystals while depleting the system of β'-2 MC_POP:PPP and β'-2 PPP crystals. This loss was further exacerbated by the addition of dispersed particles to the point where PPP was completely incorporated as MC and β'-2 PPP crystals were eliminated. While heterogeneous nucleation tends to favor kinetic products of fat crystallization, the interactions between shear and surface chemistry varied between crystal types.     

Crystallization behavior and isothermal crystallization kinetics of PLLA blended with ionic liquid, 1‐butyl‐3‐methylimidazolium dibutylphosphate

The crystallization behavior and isothermal crystallization kinetics of neat poly(l ‐lactic acid) (PLLA) and PLLA blended with ionic liquid (IL), 1‐butyl‐3‐methylimidazolium dibutylphosphate, were researched by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WXRD). Similar to the non‐isothermal crystallization behavior of neat PLLA, when PLLA melt was cooled from 200 to 20°C at a cooling rate of 10°C min^?1, no crystallization peak was detected yet with the incorporation of IL. However, the glass transition temperature and cold crystallization temperature of PLLA gradually decreased with the increase of IL content. It can be attributed to the significant plasticizing effect of IL, which improved the chain mobility and cold crystallization ability of PLLA. Isothermal crystallization kinetics was also analyzed by DSC and described by Avrami equation. For neat PLLA and IL/PLLA blends, the Avrami exponent n was almost in the range of 2.5–3.0. It is found that t_1/2 reduced largely, and the crystallization rate constant k increased exponentially with the incorporation of IL. These results show that the IL could accelerate the overall crystallization rate of PLLA due to its plasticizing effect. In addition, the dependences of crystallization rate on crystallization temperature and IL content were discussed in detail according to the results obtained by DSC and POM measurements. It was verified by WXRD that the addition of IL could not change the crystal structure of PLLA matrix. All samples isothermally crystallized at 100°C formed the α‐form crystal. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41308.     

Effect of MWNTs concentration and cooling rate on the morphological,structural, and electrical properties of non‐isothermally crystallized PEN/MWNT nanocomposites

The effect of multiwall carbon nanotubes (MWNT) concentration and cooling rate on the morphological, structural and electrical properties of non‐isothermally crystallized Poly(ethylene naphthalate) nanocomposites (PEN/MWNT) was studied. PEN/MWNT nanocomposites containing 1 and 2 wt % of nanotubes were prepared by melt blending in a mini twin screw extruder. Nanocomposite samples with different degree of crystallinity (X_c) were obtained via non‐isothermally crystallization at cooling rates of 2, 10, 20, and 300°C min^?1. In this study it was demonstrated that carbon nanotubes and cooling rate strongly influence morphological and structural characteristics of PEN. Calorimetric results showed that the peak crystallization temperature (T_c) of PEN nanocomposites was increased ～9° through heterogeneous nucleation with respect to pure PEN. X‐ray diffraction revealed that carbon nanotubes modify the crystalline structure of PEN favoring the formation of β‐crystals, and this effect increases with the nanotubes content. On the basis of X‐ray scattering analysis, the variation of lamellar thickness revealed that nanotubes promote the formation of lamellar crystals with average thickness of 20 nm at different cooling rates. These structural and morphological changes play an important role on the electrical properties of nanocomposites. It was found that higher concentration of nanotubes and crystallinity promotes electrical conductivity of nanocomposites in the order of semiconductors (until 1 × 10^?4 S cm^?1) as well as permittivity of 20 at different tested frequencies. This may due to the interconnected networks of nanotubes throughout the crystalline structure formed in PEN nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41765.     

Dynamic crystallization of polypropylene and wood‐based composites

Thermoplastic composites made of an isotactic polypropylene (iPP) matrix and woodflour (WF) were prepared by melt‐blending, using twin‐screw extrusion and injection molding. Up to 20 wt % of the composite was composed of WF. The incorporation of an interfacial agent made of an ethylene/methacrylic acid copolymer to iPP and WF, PP/WF, binary blends causes a compatibilization effect that becomes evident due to a reduction in the crystallization temperature of PP. In both the binary composites and the compatibilized or ternary composites, the PP adopts an α or monoclinic structure when crystallization occurs from the melt under dynamic conditions at cooling rates between 1 and 20°C min^?1. On the other hand, X‐ray diffraction analysis using synchrotron radiation of the injection‐molded samples demonstrates the existence of a β or trigonal form in the binary as well as the ternary PP/WF composites. They reach k_β levels between 0.18 and 0.25, which can be interpreted as the co‐operation between a reduction of the crystallization rate and the shear effect induced during the injection. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6028–6036, 2006     

Crystallization kinetics and melting behaviour of microbial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

Isothermal and non‐isothermal crystallization kinetics of microbial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐3HHx)] was investigated by differential scanning calorimetry (DSC) and ¹³C solid‐state nuclear magnetic resonance (NMR). Avrami analysis was performed to obtain the kinetic parameters of primary crystallization. The results showed that the Avrami equation was suitable for describing the isothermal and non‐isothermal crystallization processes of P(3HB‐3HHx). The equilibrium melting temperature of P(3HB‐3HHx) and its nucleation constant of crystal growth kinetics, which were obtained by using the Hoffman–Weeks equation and the Lauritzen–Hoffmann model, were, respectively, 121.8 °C and 2.87 × 10⁵ K² when using the empirical ‘universal’ values of U* = 1500 cal mol^?1. During the heating process, the melting behaviour of P(3HB‐3HHx) for both isothermal and non‐isothermal crystallization showed multiple melting peaks, which was the result of melting recrystallization. The lower melting peak resulted from the melting of crystals formed during the corresponding crystallization process, while the higher melting peak resulted from the recrystallization that took place during the heating process. Copyright © 2005 Society of Chemical Industry     

Isothermal crystallization kinetics of polypropylene in melt‐mixed composites of polypropylene and multi‐walled carbon nanotubes

The isothermal crystallization behaviour of the polypropylene (PP) phase in PP/multi‐walled carbon nanotubes (MWCNTs) composites has been investigated via differential scanning calorimetric analysis, which showed the influence of the varying dispersion level of MWCNTs in the respective PP matrix. PP/MWCNTs composites were prepared via melt‐blending technique, wherein two different grades of MWCNTs of varying average “agglomerate” size and varying entanglements (N‐MWCNTs and D‐MWCNTs) were utilized. Furthermore, the influence of melt‐viscosity of the PP phase was investigated on the crystallization kinetics of the PP/MWCNTs composites. Heterogeneous nucleation ability of MWCNTs has resulted in a decrease in half time of crystallization (t _1/2) from ～14 min for pure PP to ～6 min for PP/N‐MWCNTs and ～11 min for PP/D‐MWCNTs composites at 1 wt% of MWCNTs at 132 °C. Overall rate of crystallization (k) has significantly increased to 4.9 × 10^?2 min^?1 for PP/N‐MWCNTs composite as compared with 6.2 × 10^?3 min^?1 for PP/D‐MWCNTs composite at 0.5 wt% of MWCNTs at 132 °C. Moreover, the effect of a novel organic modifier, Li‐salt of 6‐amino hexanoic acid along with a compatibilizer (PP‐g‐MA) has also been investigated on the crystallization kinetics of the PP phase in PP/MWCNTs composites. POLYM. ENG. SCI., 57:1136–1146, 2017. © 2017 Society of Plastics Engineers     

The turning point on plots of log ϕ and log t of Mo's equation

BACKGROUND: Mo's equation based on the Avrami equation and Ozawa equation has been successfully used in non‐isothermal crystallization kinetics by many researchers. However, in recent years we have found that plots of log ?–log t of Mo's equation are not straight lines, but there appears a turning point at ? = 7 °C min^?1 or so. The aim of this article is to analyze in detail the reason for the occurrence of this turning point by studying the non‐isothermal crystallization of poly(vinylidene fluoride) (PVDF) using differential scanning calorimetry. RESULTS: A turning point at about 7 °C min^?1 appeared on plots of log ?–log t. The cooling rate where the turning point occurred showed little change with increasing relative crystallinity, but the temperature decreased. It is noted that this turning‐point temperature is lower than transition temperature of regime I → II reported for PVDF. CONCLUSION: We deemed that the occurrence of turning points on plots of log ?–log t of Mo's equation can be ascribed to the different crystallization regimes based on the Hoffman nucleation theory, and presumed that the turning point corresponded to transition of regime I → II. Finally, we considered that Mo's equation should be analyzed using two beelines, instead of one beeline. Copyright © 2009 Society of Chemical Industry     

Non‐isothermal crystallization of polypropylene with sorbitol‐type nucleating agents at cooling rates used in processing

Sorbitol‐type nucleating agents used as clarifiers for polypropylene (PP) show a complex interplay of phase and crystallization behavior. To study the crystallization behavior, cooling measurements were performed by fast scanning calorimetry using rates between 10 and 4000 K s^?1. These rates correspond to cooling rates used in processing. These measurements were combined with conventional differential scanning calorimetry (DSC) measurements at 10 K min^?1. The optical properties were characterized by haze measurements. For this investigation the commercially available clarifiers 1,3:2,4‐bis(3,4‐dimethylbenzylidene)sorbitol and 1,2,3‐tridesoxy‐4,6:5,7‐bis‐O‐[(4‐propylphenyl)methylene]nonitol were added to PP in various amounts up to 0.6 wt%. At relatively slow cooling rates only a single crystallization process was observed. In contrast, fast cooling leads to a complex crystallization behavior with up to four different crystallization processes. It was found that the temperature of the main crystallization process during fast cooling correlates with the optical properties from haze measurements. Finally, the cooling rate dependence of the different crystallization processes is discussed in terms of nucleating efficiency of the clarifiers. We conclude that the results of conventional DSC measurements cannot be extrapolated in a simple way to describe the nucleation activity of nucleating agents at cooling conditions relevant during processing. © 2018 Society of Chemical Industry     

Enzymatic Synthesis of 1‐Alkyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate Using a Novel Lysoplasmalogen‐Specific Phopholipase D

Many phospholipase Ds (PLDs) are known to catalyze transphosphatidylation as well as hydrolysis of phospholipids. Transphosphatidylation of lysoplasmalogen (LyPls)‐specific phospholipase D (LyPls‐PLD), which catalyzes hydrolysis of ether lysophospholipids such as LyPls and 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine (Lyso‐PAF), still remains unclear. This study aims to reveal the transphosphatidylation activity of LyPls‐PLD, that is, the production of cyclic ether lysophospholipid. The enzymatic reaction is conducted in a buffer system, and the reaction products of a novel LyPls‐PLD from Thermocrispum sp. are investigated using mass spectrometry (MS). MS analyses demonstrate the reaction products to consist of 100% 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate (cLyPA) and choline from Lyso‐PAF; however, 1‐alkenyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate from 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine and 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphoethanolamine is not produced. These results are expected to help in elucidating the catalytic mechanism of LyPls‐PLD, that is, the rate‐limiting step, and indicate LyPls‐PLD to be useful for the one‐pot synthesis of cLyPA. Practical Applications: A novel phospholipase D, LyPls‐PLD, can exclusively synthesize cLyPA from Lyso‐PAF using a one‐step enzymatic reaction without an organic solvent. cLyPA could be expected to show bioactivities similar to those of cyclic phosphatidic acid, which promotes normal cell differentiation, hyaluronic acid synthesis, antiproliferative activity in fibroblasts, and inhibitory activity toward cancer cell invasion and metastasis.     

Production of α‐amylase under solid‐state fermentation utilizing coffee waste

Coffee industry substrates such as coffee pulp, coffee cherry husk, silver skin, spent coffee and mixtures of these coffee wastes (MC) were evaluated for their efficacy as sole carbon source for the synthesis of α‐amylase in solid‐state fermentation (SSF) using a fungal strain of Neurospora crassa CFR 308. For SSF with coffee pulp and with MC, α‐amylase activity of 3908 U g^?1 ds (units per gram of dry substrate) and 3870 U g^?1 ds, respectively, was observed. Parameters such as moisture (60%), pH (4.6), temperature (28 °C), particle size (1.0 mm), inoculum size (10⁷ spores g^?1 ds), and fermentation time (5 days) were optimized for enzyme synthesis, wherein 4981 and 4324 U g^?1 U g^?1 ds of α‐amylase activity was obtained in SSF with coffee pulp and MC, respectively. The enzyme production was further improved when the substrates were subjected to pre‐treatment by steaming. Accordingly, maximum α‐amylase activity of 7084 U g^?1 ds and 6342 U g^?1 ds was obtained with steam‐pretreated coffee pulp and MC, respectively, demonstrating them to be excellent sole carbon sources for synthesis of α‐amylase production. Copyright © 2009 Society of Chemical Industry     

Efficient Production of 1,3-Dioleoyl-2-Palmitoylglycerol through Rhodococcus opacus Fermentation

1,3-Dioleoyl-2-palmitoylglycerol (OPO) is the main triacylglycerol species in human milk-fat substitute. The production of OPO is of considerable research interest. In this study, a new strategy for producing OPO by fermentation with R. opacus is proposed. Chemically Interesterified fat (high oleic acid sunflower oil/hydrogenated palm oil 1.73:1 w/w), or a mixture of ethyl oleate/ethyl palmitate 2:1 (w/w) as a starting material. The highest biomass and oil content obtained were 3.3 g L⁻¹ and 40.2% (dry cell weight), respectively. The yield of OPO was 0.62 g L⁻¹. The fatty acid composition of produced OPO was 55.7–59.7% 18:1 and 28.3–29.8% 16:0, and the sn-2 position was predominantly 16:0 (64.7–74.5%). ¹³C-nuclear magnetic resonance analysis showed that the sn-1,3 and sn-2 positions were predominately esterified by 18:1 and 16:0, respectively. OPO (47.1%), OPL (13.9%), PPO (13.1%), and PPoO (16:0–16:1–18:1) (10.3%) were the most abundant triacylglycerol species.