Microbial conversion of androst‐1,4‐dien‐3,17‐dione by Mucor racemosus to hydroxysteroid‐1,4‐dien‐3‐one derivatives

BACKGROUND: A large number of bacterial, fungal and microalgal species are able to bio‐transform steroid compounds. Among them, fungi from the Mucor genus have been shown to mediate hydroxylation, oxidation, and desaturation by the double bond formation and epoxidation of various steroid substances. Mucor racemocus has not been studied for its ability to modify androst‐1,4‐dien‐3,17‐dione, a pharmaceutically important steroid precursor. RESULTS: The filamentous fungus M. racemosus was applied for bioconversion of androst‐1,4‐dien‐3,17‐dione (ADD, I ) in a 5‐day fermentation. Microbial metabolites were purified chromatographically and identified on the basis of their spectral data as 17β‐hydroxyandrost‐1,4‐dien‐3‐one ( II ), 14α‐hydroxyandrost‐1,4‐dien‐3,17‐dione ( III ), 15α‐hydroxyandrost‐1,4‐dien‐3,17‐dione ( IV ), 15α,17β‐dihydroxyandrost‐1,4‐dien‐3‐one ( V ), 14α,17β‐dihydroxyandrost‐1,4‐dien‐3‐one ( VI ), and 6β,17β‐dihydroxyandrost‐1,4‐dien‐3‐one ( VII ). CONCLUSION: Observed modifications included hydroxylation at C‐6β, C‐14α, C‐15α positions and 17‐carbonyl reduction. The best fermentation conditions for production of hydroxysteroid‐1,4‐dien‐3‐one derivatives were found to be 25 °C at 150 rpm for 5 days with a substrate concentration of 0.5 g L^?1. Copyright © 2009 Society of Chemical Industry     

Lecithin‐enhanced biotransformation of cholesterol to androsta‐1,4‐diene‐3,17‐dione and androsta‐4‐ene‐3,17‐dione

A biotransformation process using Mycobacterium sp was studied for androsta‐1, 4‐diene‐3,17‐dione (ADD) and androsta‐4‐ene‐3,17‐dione (AD) production from cholesterol. Cholesterol has a poor solubility in water (～1.8 mg dm^?3 at 25 °C), which makes it difficult to use as the substrate for biotransformation. Lecithin is a mixture of phospholipids of phosphatidylcholine (PC) and phosphatidylethanolamine (PE), which behave like surfactants and can form planar bi‐layer structures in an aqueous medium. Therefore, a small amount of lecithin (<1 g dm^?3) can be used to form stable colloids with cholesterol at a relatively high concentration (20 g dm^?3) in water. In this work, an energy density of 1000 J cm^?3 from sonication was provided to overcome the self‐association of cholesterol and to generate a stable lecithin–cholesterol suspension that could be used for enhanced biotransformation. The lecithin–cholesterol suspension was stable and could withstand typical autoclaving conditions (121 °C, 15 psig, 20 min). In contrast to conventional surfactants, such as Tween 80, that are commonly used to help solubilize cholesterol, lecithin did not change the surface tension of the aqueous solution nor cause any significant foaming problem. Lecithin was also biocompatible and showed no adverse effect on cell growth. Compared with the medium with Tween 80 as the cholesterol‐solubilizing agent, lecithin greatly improved the biotransformation process in regard to its final product yield (～59% w/w), productivity (0.127–0.346 g dm^?3 day^?1), ADD/AD ratio (6.7–8), as well as the long‐term process stability. Cells can be reused in repeated batch fermentations for up to seven consecutive batches, but then lose their bioactivity due to aging problems, possibly caused by product inhibition and nutrient depletion. © 2002 Society of Chemical Industry     

Microbial conversion of sterol‐containing soybean oil production waste

Soybean extract residue (scum), a waste of soybean oil production, was examined as a raw material for C₁₇‐ketosteroid production. As a model process, its bioconversion to 9α‐hydroxyandrost‐4‐ene‐3,17‐dione (9‐OH‐AD) by Mycobacterium sp VKM Ac‐1817D was studied. The content of transformable sterols (sitosterol, stigmasterol and campesterol) in scum was estimated at ～14%. The bioconversion of scum to 9‐OH‐AD was characterized by a long lag‐period (300–350 h) followed by 9‐OH‐AD accumulation. The microbial or chemical elimination of fatty non‐identified components resulted in sterol‐enriched scum preparations. Effective conversion of these preparations by Mycobacterium sp was demonstrated: 9‐OH‐AD molar yield ～65% was reached at 60 h from the scum preparation containing 10 g dm^?3 transformable sterols. The process productivity was comparable with that for high quality‐sitosterol of wood origin (tall‐oil sitosterol). Copyright © 2004 Society of Chemical Industry     

Microwave‐assisted rapid polycondensation reaction of 4‐(4′‐acetamidophenyl)‐1,2,4‐triazolidine‐3,5‐dione with diisocyanates

4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione was reacted with 1 mol of acetyl chloride in dry N,N‐dimethylacetamide (DMAc) at ?15°C and 4‐(4′‐acetamidophenyl)‐1,2,4‐triazolidine‐3,5‐dione [4‐(4′‐acetanilido)‐1,2,4‐triazolidine‐3,5‐dione] (APTD) was obtained in high yield. The reaction of the APTD monomer with excess n‐isopropylisocyanate was performed at room temperature in DMAc solution. The resulting bis‐urea derivative was obtained in high yield and was finally used as a model for the polymerization reaction. The step‐growth polymerization reactions of monomer APTD with hexamethylene diisocyanate, isophorone diisocyanate, and tolylene‐2,4‐diisocyanate were performed under microwave irradiation and solution polymerization in the presence of pyridine, triethylamine, or dibutyltin dilaurate as a catalyst. Polycondensation proceeded rapidly, compared with conventional solution polycondensation; it was almost completed within 8 min. The resulting novel polyureas had an inherent viscosity in the range of 0.07–0.17 dL/g in dimethylformamide or sulfuric acid at 25°C. These polyureas were characterized by IR, ¹H‐NMR, elemental analysis, and thermogravimetric analysis. The physical properties and structural characterization of these novel polyureas are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2103–2113, 2004     

Polymerization of 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione with diisocyanates

4‐(4′‐Aminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( 1 ) was reacted with 1,8‐naphthalic anhydride ( 2 ) in a mixture of acetic acid and pyridine (3 : 2) under refluxing temperature and gave 4‐(4′‐N‐1,8‐naphthalimidophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( NIPTD ) ( 3 ) in high yield and purity. The compound NIPTD was reacted with excess n‐propylisocyanate in N,N‐dimethylacetamide solution and gave 1‐(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐triazolidine‐3,5‐dione ( 4 ) and 1,2‐bis(n‐propylamidocarbonyl)‐4‐[4′‐(1,8‐naphthalimidophenyl)]‐1,2,4‐ triazolidine‐3,5‐dione ( 5 ) as model compounds. Solution polycondensation reactions of monomer 3 with hexamethylene diisocyanate ( HMDI ), isophorone diisocyanate ( IPDI ), and tolylene‐2,4‐diisocyanate ( TDI ) were performed under microwave irradiation and conventional solution polymerization techniques in different solvents and in the presence of different catalysts, which led to the formation of novel aliphatic‐aromatic polyureas. The polycondensation proceeded rapidly, compared with conventional solution polycondensation, and was almost completed within 8 min. These novel polyureas have inherent viscosities in a range of 0.06–0.20 dL g^?1 in conc. H₂SO₄ or DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2861–2869, 2003     

Preparation and characterization of new photoactive polyamides containing 4‐(4‐dimethylaminophenyl)urazole units

4‐(4‐dimethylaminophenyl)‐1,2,4‐triazolidine‐3,5‐dione ( DAPTD ) was prepared from 4‐dimethylaminobenzoic acid in five steps. The compound DAPTD was reacted with excess acetyl chloride in N,N‐dimethylacetamide (DMAc) solution and gave 1,2‐bisacetyl‐4‐[4‐(dimethylaminophenyl)]‐1,2,4‐triazolidine‐3,5‐dione as a model compound. Solution polycondensation reactions of monomer with succinyl chloride (SucC), suberoyl chloride (SubC), and sebacoyl chloride (SebC) were performed under conventional solution polymerization techniques in the presence of triethylamine and pyridine as a catalyst in N‐methylpyrrolidone (NMP) and led to the formation of novel aliphatic polyamides. These novel polyamides have inherent viscosities in the range of 0.09–0.21 dL/g in N,N‐dimethylformamide (DMF) at 25°C. Fluorimetric studies of the model compound as well as polymers were performed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 947–954, 2007     

Thiol‐ene photofunctionalization of 1,4‐polymyrcene

1,4‐Polymyrcene was synthesized by anionic polymerization of β‐myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3‐mercaptopropionate, butyl 3‐mercaptopropionate, ethyl 2‐mercaptopropionate and 2‐methyl‐2‐propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4‐polymyrcene decreased in the order 1° thiol (ca 95%) > 2° thiol (ca 80%) > 3° thiol (<5%), due to the reversibility of the thiol‐ene reaction. Remarkably, thiol addition to the side‐chain double bonds was 8 ? 10 times (1° thiol) or 24 times (2° thiol) faster than to the main‐chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10‐fold excess of thiol with respect to myrcene units, the thiol‐ene addition was accompanied by chain coupling reactions, which in the extreme case of 3° thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl‐thioglycolate‐functionalized 1,4‐polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. © 2018 Society of Chemical Industry     

Synthesis of Amino Acid Conjugates and Further Derivatives of 3α‐Hydroxylup‐20(;29)ene‐23,28‐dioic acid

Triterpenes of betulinic acid type exhibit many interesting biological activities. Therefore a series of new 3α‐hydroxy‐lup‐20(29)‐ene‐23,28‐dioic acid derivatives 2a—22 with putative pharmacological activities were synthesized. As starting compounds 3α‐hydroxy‐lup‐20(29)‐ene‐23,28‐dioic acid ( 1a ), isolated from Schefflera octophylla, or its 3‐O‐acetyl derivative 1b were used. Mono‐ and diesters ( 2a—b from 1a , and 4d from 4c ) were prepared with CH₂N₂. Oxidation of the isopropenyl side chain with OsO₄ yielded the 20,29‐diols ( 4a—b from 1b , and 19 from 17 ), which were in the case of 4b further transformed to the 29‐norketones 8a/mdash;b . Oxidation of the isopropenyl side chain with m‐chloroperbenzoic acid afforded the 20,29‐epoxide 12 (from 1b ) and the 29‐aldehydes and a‐hydroxy aldehydes ( 13a—c from 2a, 14a—c from 2b , and 16a—c from 15a ). Ring A was modified by a tosylation—elimination sequence using p‐TsCl/NaOAc, which afforded diolefin 15a (from 2a ) with Δ^2,20(29) double bonds or 23‐nor‐Δ^3,20(29)diolefin 17 (from 1a ). Compounds 4b, 4c , and 8a were coupled with L ‐methionin, L ‐phenylalanin, L ‐alanin, L ‐serin, and L ‐glutaminic acid via amide bonds at positions 23 and 28 to afford the amino acid conjugates 5a—7b and 9a—11 .     

Synthesis of novel azo‐containing polyureas derived from 4‐[4′‐(2‐hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione

4‐[4′‐(2‐Hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione ( HNAPTD ) ( 1 ) has been reacted with excess amount of n‐propylisocyanate in DMF (N,N‐dimethylformamide) solution at room temperature. The reaction proceeded with high yield, and involved reaction of both N? H of the urazole group. The resulting bis‐urea derivative 2 was characterized by IR, ¹H‐NMR, elemental analysis, UV‐Vis spectra, and it was finally used as a model compound for the polymerization reaction. Solution polycondensation reactions of monomer 1 with Hexamethylene diisocyanate ( HMDI ) and isophorone diisocyanate ( IPDI ) were performed in DMF in the presence of pyridine as a catalyst and lead to the formation of novel aliphatic azo‐containing polyurea dyes, which are soluble in polar solvents. The polymerization reaction with tolylene‐2,4‐diisocyanate ( TDI ) gave novel aromatic polyurea dye, which is insoluble in most organic solvents. These novel polyureas have inherent viscosities in a range of 0.15–0.22 g dL^?1 in DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3177–3183, 2001     

Synthesis and properties of polyamides based on 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐hexahydro‐4,7‐methanoindan

A new diamine 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐hexahydro‐4,7‐methanoindan ( 3 ) was prepared through the nucleophilic displacement of 5,5′‐bis(4‐hydroxylphenyl)‐hexahydro‐4,7‐methanoindan ( 1 ) with p‐halonitrobenzene in the presence of K₂CO₃ in N,N‐dimethylformamide (DMF), followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of new polyamides were synthesized by the direct polycondensation of diamine 3 with various aromatic dicarboxylic acids. The polymers were obtained in quantitative yields with inherent viscosities of 0.76–1.02 dl g⁻¹. All the polymers were soluble in aprotic dipolar solvents such as N,N‐dimethylacetamide (DMAc) and N‐methyl‐2‐pyrrolidone (NMP), and could be solution cast into transparent, flexible and tough films. The glass transition temperatures of the polyamides were in the range 245–282 °C; their 10% weight loss temperatures were above 468 °C in nitrogen and above 465 °C in air. © 2000 Society of Chemical Industry     

Dehydrogenation of 11α‐hydroxy‐16α, 17‐epoxyprogesterone by encapsulated Arthrobacter simplex cells in an aqueous/organic solvent two‐liquid‐phase system

BACKGROUND: Arthrobacter simplex cells immobilised in sodium cellulose sulfate/poly‐dimethyl‐diallyl‐ammonium chloride microcapsules were used for the microbial dehydrogenation of 11α‐hydroxy‐16α,17‐epoxyprogesterone to 11α‐hydroxy‐16α,17α‐epoxypregn‐1,4‐diene‐3,20‐dione in an aqueous/organic solvent two‐liquid‐phase system, which is a key reaction in the production of glucocorticoid pharmaceuticals. The aim of the study was to establish a suitable aqueous/organic solvent two‐liquid‐phase system for performing semi‐continuous production in an airlift loop reactor by encapsulated A. simplex cells with the addition of suitable surfactants to achieve a higher yield of the product. RESULTS: n‐Hexane was selected as the most suitable organic solvent. In optimised Tween‐80 emulsion feed mode the conversion in the airlift loop reactor was as high as 97.54% when the time of reaction was 2 h, and the reaction time was greatly shortened. In semi‐continuous production the cultivation with immobilised cells was carried out for five batches in total. The conversion in each batch was above 95% and the enzymatic activity still remained quite high after five batches of biotransformation. CONCLUSION: The results showed that performing the conversion by this method shortened the reaction time and increased the productivity, thus demonstrating the great potential of the method for the dehydrogenation of 11α‐hydroxy‐16α,17‐epoxyprogesterone. Copyright © 2008 Society of Chemical Industry     

High‐temperature piezoelectric properties of 0‐3 type CaBi4Ti4O15:x wt%BiFeO3 composites

The 0‐3 type CaBi₄Ti₄O₁₅:30 wt%BiFeO₃ composite shows much better high‐temperature piezoelectric properties than the single‐phase CaBi₄Ti₄O₁₅ or BiFeO₃ ceramics. The composite with 0‐3 type connectivity exhibits a high density of 7.01 g/cm³, a saturated polarization of 21.5 μC/cm² and an enhanced piezoelectric d₃₃ of 25 pC/N. After the poled composite was annealed at 600°C, its d₃₃ is 21 pC/N at room temperature. Resistance of the composite decreases slowly from 10⁹ ohm at 20°C to ~10⁵ ohm at 500°C. Furthermore, the poled composite shows strong radial and thickness dielectric resonances at 20°C‐500°C.     

Synthesis and characterization of new cardo poly(ether imide)s derived from 9,9‐bis [4‐(4‐aminophenoxy)phenyl]xanthene

A series of new cardo poly(ether imide)s bearing flexible ether and bulky xanthene pendant groups was prepared from 9,9‐bis[4‐(4‐aminophenoxy)phenyl]xanthene with six commercially available aromatic tetracarboxylic dianhydrides in N,N‐dimethylacetamide (DMAc) via the poly(amic acid) precursors and subsequent thermal or chemical imidization. The intermediate poly(amic acid)s had inherent viscosities between 0.83 and 1.28 dL/g, could be cast from DMAc solutions and thermally converted into transparent, flexible, and tough poly(ether imide) films which were further characterized by X‐ray and mechanical analysis. All of the poly(ether imide)s were amorphous and their films exhibited tensile strengths of 89–108 MPa, elongations at break of 7–9%, and initial moduli of 2.12–2.65 GPa. Three poly(ether imide)s derived from 4,4′‐oxydiphthalic anhydride, 4,4′‐sulfonyldiphthalic anhydride, and 2,2‐bis(3,4‐dicarboxyphenyl))hexafluoropropane anhydride, respectively, exhibited excellent solubility in various solvents such as DMAc, N,N‐dimethylformamide, N‐methyl‐2‐pyrrolidinone, pyridine, and even in tetrahydrofuran at room temperature. The resulting poly(ether imide)s with glass transition temperatures between 286 and 335°C had initial decomposition temperatures above 500°C, 10% weight loss temperatures ranging from 551 to 575°C in nitrogen and 547 to 570°C in air, and char yields of 53–64% at 800°C in nitrogen. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Organosoluble and light‐colored fluorinated polyimides based on 1,1‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐1‐phenylethane and various aromatic dianhydrides

To investigate the CF₃ group affecting the coloration and solubility of polyimides (PI), a novel fluorinated diamine 1,1‐bis[4‐(4‐amino‐2‐ trifluoromethylphenoxy)phenyl]‐1‐phenylethane (2) was prepared from 1,1‐ bis(4‐hydrophenyl)‐1‐phenylethan and 2‐chloro‐5‐nitrobenzotrifluoride. A series of light‐colored and soluble PI 5 were synthesized from 2 and various aromatic dianhydrides 3a–f using a standard two‐stage process with thermal 5a– f(H) and chemical 5a–f(C) imidization of poly(amic acid). The 5 series had inherent viscosities ranging from 0.55 to 0.98 dL/g. Most of 5a–f(H) were soluble in amide‐type solvents, such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐ dimethylacetamide (DMAc), and N,N‐dimethylformamide (DMF), and even soluble in less polar solvents, such as m‐Cresol, Py, Dioxane, THF, and CH₂Cl₂, and the 5(C) series was soluble in all solvents. The GPC data of the 5a–f(C) indicated that the Mn and Mw values were in the range of 5.5–8.7 × 10⁴ and 8.5–10.6 × 10⁴, respectively, and the polydispersity index (PDI) Mw /Mn values were 1.2–1.5. The PI 5 series had excellent mechanical properties. The glass transition temperatures of the 5 series were in the range of 232–276°C, and the 10% weight loss temperatures were at 505–548 °C in nitrogen and 508–532 °C in air, respectively. They left more than 56% char yield at 800°C in nitrogen. These films had cutoff wavelengths between 356.5–411.5 nm, the b* values ranged from 5.0–71.1, the dielectric constants, were 3.11–3.43 (1MHz) and the moisture absorptions were in the range of 011–0.40%. Comparing 5 containing the analogous PI 6 series based on 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐ phenylethane (BAPPE), the 5 series with the CF₃ group showed lower color intensity, dielectric constants, and better solubility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2399–2412, 2005     

Synthesis and characterization of new cardo poly(bisbenzothiazole)s from 1,1‐bis(4‐amino‐3‐mercaptophenyl)‐4‐tert‐butylcyclohexane dihydrochloride

A new monomer 1,1‐bis(4‐amino‐3‐mercaptophenyl)‐4‐tert‐butylcyclohexane dihydrochloride, bearing the bulky pendant 4‐tert‐butylcyclohexylidene group, was synthesized from 4‐tert‐butylcyclohexanone in three steps. Its chemical structure was characterized by ¹H NMR, ¹³C NMR, MS, FTIR, and EA. Aromatic poly(bisbenzothiazole)s (PBTs V) were prepared from the new monomer and five aromatic dicarboxylic acids by direct polycondensation. The inherent viscosities were in the range of 0.63–2.17 dL/g. These polymers exhibited good solubility and thermal stability. Most of the prepared PBTs V were soluble in various polar solvents. Thermogravimetric analysis showed the decomposition temperatures at 10% weight loss that were in the range of 495–534°C in nitrogen. All the PBTs V, characterized by X‐ray diffraction, were amorphous. The UV absorption spectra of PBTs V showed a range of λ_max from 334 to 394 nm. All the PBTs V prepared had evident fluorescence emission peaks, ranging from 423 to 475 nm with different intensity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2000–2008, 2006     

Hydrogenation of Carbon Dioxide to Formate Catalyzed by a Copper/1,8‐Diazabicyclo[5.4.0]undec‐7‐ene System

Hydrogenation of carbon dioxide to formate was achieved using copper (Cu) catalysts in the presence of strong organic bases including amidines and guanidines. Specifically, 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) proved to be effective for the transformation of a 1:1 mixture of hydrogen and carbon dioxide into its formate salt under increased pressure in the presence of various Cu(I) and Cu(II) salts at 100 °C. A novel complex derived from copper iodide and DBU equally promoted the same reaction, indicating that DBU–Cu species are involved as real catalysts in this hydrogenation.

     

Tailoring the surface architecture of poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) scaffolds

This study was designed to determine whether the surface modifications of the various poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) [P(3HB‐co‐4HB)] copolymer scaffolds fabricated would enhance mouse fibroblast cells (L929) attachment and proliferation. The P(3HB‐co‐4HB) copolymer with a wide range of 4HB monomer composition (16–91 mol %) was synthesized by a local isolate Cupriavidus sp. USMAA1020 by employing the modified two‐stage cultivation and by varying the concentrations of 4HB precursors, namely γ‐butyrolactone and 1,4‐butanediol. Five different processing techniques were used in fabricating the P(3HB‐co‐4HB) copolymer scaffolds such as solvent casting, salt‐leaching, enzyme degradation, combining salt‐leaching with enzyme degradation, and electrospinning. The increase in 4HB composition lowered melting temperatures (T_m) but increased elongation to break. P(3HB‐co‐91 mol % 4HB) exhibited a melting point of 46°C and elongation to break of 380%. The atomic force analysis showed an increase in the average surface roughness as the 4HB monomer composition increased. The mouse fibroblasts (L929) cell attachment was found to increase with high 4HB monomer composition in copolymer scaffolds. These results illustrate the importance of a detailed characterization of surface architecture of scaffolds to provoke specific cellular responses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Asymmetric Michael Addition of 5 H‐Oxazol‐4‐ones to Vinyl Sulfones: Stereoselective Synthesis of Monofluorinated Analogs of 2‐Tertiary Hydroxyl‐3‐Methyl‐Substituted Carboxylic Acidl Derivatives

An asymmetric Michael addition of 5H‐oxazol‐4‐ones to vinyl sulfones has been developed. In the presence of 10 mol % of quinine‐based benzyl‐substituted thiourea as catalyst at 0 °C, the products could be obtained with excellent enantio‐ and diastereoselectivity (up to>99 % ee and>20:1 dr). 1.0 mol % of catalyst also produced the corresponding adducts with similar stereoselective results when the temperature was increased to 25 °C. The obtained adducts have been demonstrated as significant synthetic fragments to conveniently access the monofluorinated analogs of biologically important 2‐tertiary hydroxyl‐3‐methyl‐substituted carboxylic acid derivatives.

     

Synthesis,Crystal Structure,and Thermal Behavior of 3‐(4‐Aminofurazan‐3‐yl)‐4‐(4‐nitrofurazan‐3‐yl)furazan (ANTF)

The energetic material 3‐(4‐aminofurazan‐3‐yl)‐4‐(4‐nitrofurazan‐3‐yl)furazan (ANTF) with low melting‐point was synthesized by means of an improved oxidation reaction from 3,4‐bis(4′‐aminofurazano‐3′‐yl)furazan. The structure of ANTF was confirmed by ¹³C NMR spectroscopy, mass spectrometry, and the crystal structure was determined by X‐ray diffraction. ANTF crystallized in monoclinic system P2₁/c, with a crystal density of 1.785 g cm⁻³ and crystal parameters a=6.6226(9) Å, b=26.294(2) Å, c=6.5394(8) Å, β=119.545(17)°, V=0.9907(2) nm³, Z=4, μ=0.157 mm⁻¹, F(000)=536. The thermal stability and non‐isothermal kinetics of ANTF were studied by differential scanning calorimetry (DSC) with heating rates of 2.5, 5, 10, and 20 K min⁻¹. The apparent activation energy (E_a) of ANTF calculated by Kissinger's equation and Ozawa's equation were 115.9 kJ mol⁻¹ and 112.6 kJ mol⁻¹, respectively, with the pre‐exponential factor lnA=21.7 s⁻¹. ANTF is a potential candidate for the melt‐cast explosive with good thermal stability and detonation performance.     

Synthesis and characterization of photoluminescent conjugated polymer containing N‐(α‐naphthyl)‐carbazole unit

A novel luminescent conjugated polymer, poly[{9‐(α‐naphthyl)‐3,6‐divinylenecarbazolylene}‐alt‐co‐(1,4‐phenylene)] (PNVCP), bearing alternated 9‐(α‐naphthyl)‐carbazole and benzene units, was synthesized via a Wittig–Horner reaction. The solubility, thermal, and optical properties were investigated. It was soluble in common organic solvents, such as tetrahydrofuran and 1,2‐dichlororoethane. Thermogravimetric analysis and differential scanning calorimetry showed that the conjugated polymer exhibited good thermal stability up to 496°C with a glass‐transition temperature higher than 110°C. The photoluminescence properties were studied. The polymer emits blue light and the quantum yield is 93% in solution. The emission spectra exhibited an obvious solvent effect. With the increase of the polarity of the solvents, the fluorescence spectra changed obviously and appeared to be redshifted at room temperature. The redshift was more obvious in aromatic solvents than in aliphatic solvents. When N,N‐dimethylaniline was gradually added into the solution of the conjugated polymer, the emission intensity of the fluorescence decreased. In comparison, the emission intensity of the polymer showed invariability when 1,4‐dicyanobenzene was added into the polymer solution. Moreover, the fluorescence of the polymer could be effectively quenched by fullerene. Overall, the synthesized polymer is a potential candidate material for fabrication of polymeric light‐emitting devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 923–927, 2006