Fire Retardance in Polyamide‐6,6. The Effects of Red Phosphorus and Radiation‐Induced Cross‐Links

The combustion performance of polyamide‐6,6 (PA‐6,6) can be improved by the addition of red phosphorus provided it is intermolecularly cross‐linked upon irradiation with ⁶⁰Co‐γ‐rays in the presence of triallyl cyanurate (TAC). At a content of 5 wt.‐% the latter promotes cross‐linking, both in the presence and absence of O₂, by a factor of about 100. From a variety of combustion tests with samples containing red phosphorus and having been γ‐irradiated in the presence of TAC it turned out that an improved fire resistance of PA‐6,6 is achieved if the red phosphorus content is at least 7 wt.‐%. In this case test samples were self‐extinguishing and the UL 94 rating corresponded to V‐0. IR analysis of the solid residue brought about evidence for the reaction of red phosphorus with the polymer.     

Fire Retardance in Poly(butylene terephthalate). The Effects of Red Phosphorus and Radiation‐Induced Cross‐Links

Summary: The combustion performance of poly(butylene terephthalate) (PBT) can be improved by the addition of red phosphorus provided it is intermolecularly cross‐linked upon irradiation with ⁶⁰Co γ‐rays in the presence of triallyl cyanurate (TAC). At a content of 3 or 4 wt.‐% the latter significantly promotes cross‐linking in the presence of air. From combustion tests with samples containing red phosphorus (P_red) and having been γ‐irradiated in the presence of TAC it turned out that an improved fire resistance of PBT is achieved if the red phosphorus content is at least 12.5 wt.‐%. In this case test samples were self‐extinguishing and the UL 94 rating corresponded to V‐1. Product analysis and thermal gravimetric analysis revealed that P_red stimulates aromatization and charring. These processes involve the reaction of P_red with the polymer. ³¹P NMR spectroscopy revealed that the residue contained chemically bonded phosphorus.

Decomposition of anhydride groups resulting in phenyl radicals.     

Polyurethane/poly[bis(carboxylatophenoxy)phosphazene] blends and their potential as flame‐retardant materials

A functionalized polyphosphazene, poly[bis(carboxylatophenoxy)‐phosphazene], was blended with a structural polyurethane via reactive mixing of the polymer with diisocyante and diol prepolymers. The thermal stabilites of the resultant foams were analyzed by thermogravimetric analysis (TGA). The char yields at both 400°C and 600°C increased relative to the pure polyurethane upon increasing the amount of polyphosphazene from 5 wt% to 20 wt%. At higher incorporations, the char at 400°C remained the same, but the char at 600°C continued to increase. The combustion behavior of these foams was analyzed both qualitatively, by a horizontal flame test, and quantitatively, by oxygen index (OI) measurements. Both of these tests indicated an increase in flame resistance at loadings of 20 wt% and above.     

Synthesis and characterization of radio‐opaque thermosensitive poly[N‐isopropylacrylamide‐2,2′‐(ethylenedioxy)bis(ethylamine)‐2,3,5‐triiodobenzamide]

BACKGROUND: In situ gelling polymers, like poly(N‐isopropylacrylamide) (poly(NIPAAm)), have many potential medical applications due to their biocompatibility and thermosensitivity. RESULTS: Radio‐opaque thermosensitive poly(NIPAAm) grafted with 10.7 wt% 2,2′‐(ethylenedioxy)bis(ethylamine)‐2,3,5‐triiodobenzamide was successfully synthesized and characterized. The conjugated polymer showed good visibility with X‐ray fluoroscopy. The polymer had a lower critical solution temperature of 30 °C after conjugation with triiodobenzamide as determined by cloud point determination and a transition peak temperature of 33.3 ± 0.57 °C as determined by differential scanning calorimetry. CONCLUSION: The polymer synthesized was highly visible under X‐rays, based upon the percentage incorporation of triiodobenzamide. After conjugation of the NIPAAm to the triiodobenzamide through a bis(ethylamine) linkage, the resultant polymer retained lower critical solution temperature characteristics in a temperature region that makes it physiologically useful. Copyright © 2009 Society of Chemical Industry     

Fire and thermal properties of PA 66 resin treated with poly‐N‐aniline‐phenyl phosphamide as a flame retardant

In this study, a halogen‐free phosphorous‐nitrogen synergistic flame retardant, poly‐N‐aniline‐phenyl phosphamide (PDPPD), was synthesized. Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and elemental analysis data confirmed the structure of PDPPD. The essential FR PA66 was polymerized with PA66 pre‐polymer and PDPPD pre‐polymer, prepared from PDPPD and adipic acid. The limit oxygen index and UL‐94 test results of FR PA66 reached 28% and V‐0, respectively, when the contents of PDPPD pre‐polymer were 4.5 wt%. The thermo‐gravimetric and differential scanning calorimetry results demonstrated that the initial decomposition temperature of FR PA66 was 43 °C lower than that of pristine PA66 from 385 to 342 °C; however, the peak decomposition temperature was 36 °C higher than that of pure PA66 from 437 to 473 °C, when the contents of PDPPD pre‐polymer reached 4.5 wt%. Flame retardant mechanism was studied by cone calorimeter testing and SEM‐EDX, confirming that the heat release rate (HRR), total heat release (THR), and total smoke product (TSP) decreased slightly, and PDPPD followed the gas phase flame retardant mechanism. Copyright © 2016 John Wiley & Sons, Ltd.     

Blends of bacterial poly[(R)‐3‐hydroxybutyrate] with oligo[(R,S)‐3‐hydroxybutyrate]‐diol

The miscibility, melting and crystallization behaviour of poly[(R)‐3‐hydroxybutyrate], PHB, and oligo[(R,S)‐3‐hydroxybutyrate]‐diol, oligo‐HB, blends have been investigated by differential scanning calorimetry: thermograms of blends containing up to 60 wt% oligo‐HB showed behaviour characteristic of single‐phase amorphous glasses with a composition dependent glass transition, T_g, and a depression in the equilibrium melting temperature of PHB. The negative value of the interaction parameter, determined from the equilibrium melting depression, confirms miscibility between blend components. In parallel studies, glass transition relaxations of different melt‐crystallized polymer blends containing 0–20 wt% oligo‐HB were dielectrically investigated between ?70 °C and 120 °C in the 100 Hz to 50 kHz range. The results revealed the existence of a single α‐relaxation process for blends, indicating the miscibility between amorphous fractions of PHB and oligo‐HB. © 2002 Society of Chemical Industry     

Synthesis and characterization of novel wholly para‐oriented aromatic polyamide‐hydrazides containing sulfone‐ether linkages

Four novel wholly para‐oriented aromatic polyamide‐hydrazides containing flexibilizing sulfone‐ether linkages in their main chains have been synthesized from 4‐amino‐3‐hydroxy benzhydrazide (4A3HBH) with either 4,4′‐sulfonyldibenzoyl chloride (SDBC), 4,4′‐[sulfonylbis(1,4‐phenylene)dioxy]dibenzoyl chloride (SODBC), 4,4′‐[sulfonylbis(2,6‐dimethyl‐1,4‐phenylene)dioxy]dibenzoyl chloride (4MeSODBC), or 4,4′‐(1,4‐phenylenedioxy)dibenzoyl chloride (ODBC) via a low‐temperature solution polycondensation reaction. A polyamide‐hydrazide without the flexibilizing linkages is also investigated for comparison. It was synthesized from 4A3HBH and terephthaloyl chloride (TCl) by the same synthetic route. The intrinsic viscosities of the polymer ranged from 2.85 to 4.83 dL g^?1 in N,N‐dimethyl acetamide (DMAc) at 30°C and decreased with introducing the flexibilizing linkages into the polymer. All the polymers were soluble in DMAc, N,N‐dimethyl formamide (DMF), and N‐methyl‐2‐pyrrolidone (NMP), and their solutions could be cast into films with good mechanical strengths. Further, they exhibited a great affinity to water sorption. Their solubility and hydrophilicity increased remarkably by introducing the flexibilizing linkages. The polymers could be thermally cyclodehydrated into the corresponding poly(1,3,4‐oxadiazolyl‐benzoxazoles) approximately in the region of 295–470°C either in nitrogen or in air atmospheres. The flexibilizing linkages improve the solubility of the resulting poly(1,3,4‐oxadiazolyl‐benzoxazoles) when compared with poly(1,3,4‐oxadiazolyl‐benzoxazoles) free from these linkages. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ultra‐Low Fire Glass‐Free Li3FeMo3O12 Microwave Dielectric Ceramics

A new ultra‐low fire glass‐free microwave dielectric material Li₃FeMo₃O₁₂ was investigated for the first time. Single phase ceramics were obtained by the conventional solid‐state route after sintering at 540°C–600°C. The atomic packing fraction, FWHM of the A_g oxygen‐octahedron stretching Raman mode and Qf values of samples sintered at different temperatures correlated well with each other. The sample with a Lower Raman shift showed a higher dielectric constant. Interestingly, the system also showed a distinct adjustable temperature coefficient of resonant frequency (from ?84× 10^?6/°C to 25 × 10^?6/°C).     

Properties of polyamide‐zirconia nanocomposites prepared from sol‐gel technique

Transparent nanocomposites were prepared by producing zirconia network in glassy polyamide matrix using sol‐gel technique. Different amounts of tetrapropyl zirconate (TPZ) were added in polymer solution using anhydrous dimethylformamide as solvent. TPZ was hydrolyzed and condensed in situ in the matrix for the generation of inorganic networks using diethylamine. Thin and transparent films containing different proportions of zirconia were obtained by evaporating the solvent. Mechanical, dynamic mechanical thermal and morphological analyses of these films were carried out. An increase in tensile modulus was observed with the films containing zirconia contents up to 15 wt%, but the elongation at rupture was found to decrease sharply on further addition of zirconia. Toughness of the hybrid materials decreased with increased amount of zirconia. Dynamic mechanical thermal analysis (DMTA) performed on the samples indicates an increase in the glass transition temperature; 102°C with pure polyamide to 132°C with polyamide containing 15 wt% zirconia contents. The storage modulus was also found to increase with increase in zirconia proportion in the matrix. The decrease in the storage modulus of the hybrids with rise in temperature was observed to be much smaller as compared with that of pure polymer. Thermal decomposition temperatures of the hybrids were found in the range of 450–500°C. The weights of the residues left at 700°C were nearly proportional to the zirconia contents in the original hybrids. The morphological studies suggest a uniform dispersion of zirconia domains in the matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Sulfonated poly(sulfone‐pyridine‐amide)/sulfonated polystyrene/multiwalled carbon nanotube‐based fuel cell membranes

In this study, aromatic sulfonated poly(sulfone‐pyridine‐amide) (S‐PSPA) has been prepared via polycondensation of sulfonated monomer 1‐(4‐thiocarbamoylaminophenyl‐sulfonylphenyl)thiourea and 2,6‐pyridinedicarboxylic acid at high temperature. Mechanically robust and thermally stable hybrid membranes were prepared using non‐functional and functional multiwalled carbon nanotube (MWCNT) i.e., S‐PS/S‐PSPA/MWCNT‐NF and S‐PS/S‐PSPA/MWCNT via solution blending. Field emission scanning electron microscopy exhibited porous membrane structure for 0.1–0.5 wt% nanotube loading, whereas well‐aligned functional MWCNT were observed in 1 wt% loaded sample. Increasing the functional nanotube content from 0.1 to 1 wt% increased tensile strength of functional S‐PS/S‐PSPA/MWCNT hybrids from 62.19 to 65.29 MPa compared with non‐functional hybrid (53.34 MPa) and neat S‐PS/S‐PSPA. 10% decomposition temperature of S‐PS/S‐PSPA/MWCNT 0.1–1 was in the range 491–502°C, while S‐PS/S‐PSPA/MWCNT‐NF showed relatively lower thermal stability (T₁₀ 489°C). Glass transition temperature of functional S‐PS/S‐PSPA/MWCNT was also higher (201–243°C) relative to S‐PS/S‐PSPA/MWCNT‐NF (194°C). Furthermore, functional MWCNT‐based membranes had higher ion exchange capacity (IEC) 3.2–3.6 mmol/g and lower activation energies (95–36 kJ/mol). Novel functional membranes also revealed high proton conductivity 1.68–2.55 S/cm in a wide range of humidity at 80°C higher than that of perfluorinated Nafion® membrane (1.1 ×10^?1 S/cm) at 80°C (94% RH). POLYM. ENG. SCI., 55:1776–1786, 2015. © 2014 Society of Plastics Engineers     

Improving the flame retardance and melt dripping of poly(lactic acid) with a novel polymeric flame retardant of high thermal stability

A polymeric flame retardant containing phosphorus and nitrogen (PCNFR) was synthesized and characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The thermal decomposition temperatures at 10% weight loss (T_{10 wt%}) of PCNFR were around 358 °C, and the char yield at 600 °C reached about 60 wt% both in nitrogen and air by thermogravimetric analysis. The flame retarded poly(lactic acid) (PLA) composites with PCNFR were prepared. The thermogravimetric analysis results showed that PCNFR could improve the thermal stability of the flame retarded PLA composites with low loading (≤10 wt%) and at high temperature zone (≥390 °C). The condensed products from the decomposition of the flame retarded composites at 380 °C and 450 °C for different intervals were analyzed by Raman spectroscopy, and the results showed that time and temperature influenced the structure of the char residue evidently. When incorporating 30 wt% PCNFR into PLA, the limited oxygen index of the flame retarded composites reached 25.0%, and V‐0 rating was achieved. The char residues were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy in detail. Copyright © 2016 John Wiley & Sons, Ltd.     

High‐temperature‐resistant polymer gel system with metal–organic mixed cross‐linking agents

A high‐temperature (200°C)‐resistant polymer gel system was developed from partially hydrolyzed polyacrylamide (HPAM), chromium lactate (CrL), and water‐soluble phenol/formaldehyde resin (WPF) mixed cross‐linkers. Rheological measurements indicated that the gelation process of the gel system could be divided into four successive steps: induction, first cross‐linking with metal cross‐linker, secondary cross‐linking with organic cross‐linker, and stabilization. Effects of various parameters that affect the gelation time and gel strength including polymer concentration, cross‐linker concentration, salinity, pH, and the gelation temperature were evaluated. Gelant formulated with 0.5 wt % HPAM, 0.1 wt % CrL, and 0.9 wt % WPF and treated at 80°C for 48 h showed sufficient gelation time, high rigidity, and good thermal stability. Morphology observation by scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed that the gel had compact network microstructure. A cross‐linking mechanism for the gel system was proposed based on the gelation process and experimental results. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42261.     

A novel phosphorus‐containing copolyester with low melting temperature and high flame retardancy

BACKGROUND: The increasing uses of non‐woven fabrics need the development of a kind of novel flame‐retardant polyester with low melting temperature. Neopentyl glycol (NPG) and 3‐(hydroxyphenylphosphinyl)propionic acid (HPPPA) were used as the third and fourth comonomer to synthesize phosphorus‐containing poly[(ethylene terephthalate)‐co‐(neopentyl terephthalate)] (PENT) with both flame retardancy and low melting temperature. RESULTS: The chemical structure of PENT was confirmed using Fourier transform infrared, ¹H NMR, ¹³C NMR and ³¹P NMR spectroscopy. PENT displays a monomodal gel permeation chromatography curve. When the content of NPG was kept at 10 wt% and the content of HPPPA increased to 5 wt%, the melting temperature (T_m) of the resulting PENT5/10 decreases to 171.2 °C, a 34.6 °C decrease compared to that of PENT0/10 (containing no HPPPA). The flammability of the PENTs was characterized with the limiting oxygen index (LOI) test, the UL‐94 vertical test and the cone calorimeter test. The incorporation of HPPPA can significantly improve the flame retardancy of the PENTs, the LOI values of the PENTs increasing from 24.4 to 37.6, as the loading of HPPPA increases from 0 to 5 wt%. CONCLUSION: The PENTs possess both low melting temperatures and excellent flame retardancy. HPPPA can be used as fourth comonomer to improve the flame retardancy of the PENTs, while decreasing the T_m value of the copolyester. Copyright © 2009 Society of Chemical Industry     

Wetting behaviour and direct observation of thermally responsive polystyrene‐block‐poly(N‐isopropylacrylamide)‐block‐polystyrene electrospun fibres in aqueous environment

Electrospun fibres of thermally responsive triblock copolymer polystyrene‐block‐poly(N‐isopropylacrylamide)‐block‐polystyrene were prepared. Fibre morphology and swelling were studied below and above the lower critical solution temperature of poly(N‐isopropylacrylamide) (PNIPAM) using cryo‐electron microscopy. Cryo‐transmission electron microscopy showed that the fibre diameter increased up to 150% after immersion in water at 20 °C. In contrast, at 45 °C the fibre diameter increased considerably less. The sessile drop technique was used to characterize temperature‐dependent wetting of fibre mats. Contact angle (θ_CA) measurements revealed that a block copolymer fibre mat changed from hydrophobic (θ_CA > 90°) to hydrophilic (θ_CA < 90°) state within seconds after applying a water droplet on it at 20 °C. At 40 °C the initial contact angle was measured to be higher (135°) and it decreased much less than at 20 °C during the first minute of measurement. We observed using scanning electron microscopy that the electrospun fibres of the block copolymer having 77 wt% of PNIPAM lost their cylindrical shape and changed from fibres to thin sheets at both 20 and 40 °C within seconds after applying water on the fibres. Fibres having 55 wt% of PNIPAM were observed to be stable in water at both 20 and 40 °C, which resulted, surprisingly, in fibre mats with the strongest effects on thermally sensitive wetting. We discuss the surprising results and the implications that the evolution of fibre surface roughness has on the long‐term wetting behaviour, demonstrating a self‐adaptable hydrophilicity/hydrophobicity nature of the fibre mats. © 2013 Society of Chemical Industry     

Synthesis of soluble and thermally stable polyimides from 3,5‐diamino‐N‐(4‐(8‐quinolinoxy) phenyl) aniline and various dianhydrides

Three novel polyimides (PIs) having pendent 4‐(quinolin‐8‐yloxy) aniline group were prepared by polycondensation of a new diamine with commercially available tetracarboxylic dianhydrides, such as pyromellitic dianhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bicyclo[2.2.2]‐oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride. These PIs were characterized by FTIR, ¹H NMR, and elemental analysis; they had high yields with inherent viscosities in the range of 0.4–0.5 dl g⁻¹, and exhibited excellent solubility in many organic solvents such as N,N‐dimethyl acetamide, N,N′‐dimethyl formamide, N‐methyl pyrrolidone (NMP), dimethyl sulfoxide, and pyridine. These PIs exhibited glass transition temperatures (T_g) between 250 and 325° C. Their initial decomposition temperatures (T_i) ranged between 270 and 450°C, and 10% weight loss temperature (T₁₀) up to 500°C with 68% char yield at 600°C under nitrogen atmosphere. Transparent and hard polymer films were obtained via casting from their NMP solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and electro‐optical properties of novel Y‐type polyurethanes containing dioxynitrostilbene

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene (2) was prepared by the reaction of 2‐iodoethanol with 3,4‐dihydroxy‐4′‐nitrostilbene. Diol 2 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate and 1,6‐hexamethylenediisocyanate to yield novel Y‐type polyurethanes 3–5 containing dioxynitrostilbene as a non‐linear optical (NLO)‐chromophore. Polymers 3–5 were soluble in common organic solvents, such as acetone and DMF. These polymers showed thermal stability up to 280 °C in TGA thermograms with T_g values in the range of 100–143 °C in DSC thermograms. The approximate lengths of aligned NLO‐chromophores of the polymers estimated from AFM images were around 2 nm. The SHG coefficients (d₃₃) of poled polymer films were around 4.5 × 10^?8 esu. Poled polymer films had improved temporal and long‐term thermal stability owing to the hydrogen bonding of urethane linkage and the main‐chain character of the polymer structure, which are acceptable for NLO device applications. Copyright © 2004 Society of Chemical Industry     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Potassium‐catalyzed steam gasification of ash‐free lignite coal with CO2 capture

The purpose of this research was to study steam gasification of ash‐free coal integrated with CO₂ capture in the presence of a K₂O catalyst for enhancement of the key water‐gas shift reaction and promotion of hydrogen production. To achieve this goal, gasification experiments on ash‐free coal (AFC) were carried out at varying temperatures (600, 650, 675, 700, and 750 °C) with a sorbent‐to‐carbon (CaO/C) ratio of 2 and a catalyst (K₂O) loading of 0.2 g/g (20 weight percent (wt%)) in a fixed‐bed reactor equipped with a gas chromatography analyzer. The sorbent‐to‐carbon (CaO/C) ratio of 2 is based on dry and ash‐free basis. The CaO/C ratio and K₂O wt% were chosen to maximize hydrogen production based on our previously determined optimal values. The AFC was originally extracted from raw lignite coal using organic solvents, which allowed the sorption‐enhanced gasification to be conducted with minimal ash‐catalyst interactions. The effect of temperature on the yield and the initial reaction rate were investigated. The optimal reaction temperature of 675 °C was determined. Carbon balance and final carbon conversions were calculated based on the residue analysis. Activation energy was also calculated using intrinsic kinetics of the reaction. In this study, using AFC offered the potential advantage of operating the gasification process with catalyst recycle.     

Cross‐Linked Amorphous Nitrilase Aggregates for Enantioselective Nitrile Hydrolysis

A recombinant Escherichia coli strain was constructed which efficiently expressed the enantioselective nitrilase from Alcaligenes faecalis DSMZ 30030 as a hisitidine‐tagged enzyme variant under the control of a rhamnose inducible promoter. The enzyme was purified from cell extracts and used for the preparation of cross‐linked enzyme aggregates (CLEAs). The conditions for the preparation of the CLEAs were optimized using various organic solvents and cross‐linking agents and a procedure was developed which combined a precipitation with 85 % (v/v) isopropyl alcohol and a cross‐linking with 30 mM glutaraldehyde. Thus, about 80 % of the initial nitrilase activity could be incorporated into the CLEAs. The hydrolysis of racemic mandelonitrile to (R)‐mandelic acid was compared between the soluble nitrilase preparations and their CLEAs (nit‐CLEAs). The nitrilase activity in the CLEAs was at 30 °C and 60 °C about 5 times more stable than in the soluble preparations. The CLEAs could be reused 5 times with only about 10 % reduction in activity. The enantioselectivity of the nitrilase for the formation of (R)‐mandelic acid from racemic mandelonitrile decreased for both preparations with increasing temperatures (10 °C to 50 °C), but this effect was significantly less pronounced for the CLEAs. A detailed analysis of solvent effects on nitrilase enantioselectivity allowed thermodynamic insights into contributions from free energy component (activation enthalpy and entropy) to chiral preference of nitrilase in such non conventional media.