Liquid crystalline polymers V. Thermotropic liquid crystalline poly(azomethine-ether)s containing a cycloalkanone moiety in the polymer backbone

A new homologous series of thermotropic liquid crystalline poly(azomethine-ether)s was synthesized by solution polycondensation of various diformyl-alpha,omega-diphenoxyalkanes, I-VIII with 2,5-bis(m-aminobenzylidene)cyclopentanone, XI and 2,6-bis(m-aminobenzylidene)cyclohexanone, XII. The inherent viscosities of the polymers were in the range 0.34-0.75 dI g^-1. The mesomorphic properties were studied as a function of the diphenoxyalkane spacer length. Analyses by DSC and optical polarized microscopy demonstrated that the poly(azomethine-ether)s form nematic mesophases over wide temperature ranges. The poly(azomethine-ether)s based on the cyclohexanone moiety had better thermal stabilities than the corresponding poly(azomethine-ether)s based on cyclopentanone.     

The synthesis and mesomorphic properties of liquid crystals with bulky terminal groups designed for bookshelf geometry ferroelectric mixtures

The synthesis and mesomorphic properties of a systematic range of ortho difluoroterphenyls with a bulky terminal chain are detailed. The bulky terminal chain consists of either a tertiarybutyl group or a trimethylsilyl unit, each separated from the core by a short (dimethylene) chain, with the other terminal chain being either octyloxy or heptyl. The synthesis of the materials was affected efficiently using a combination of low temperature lithiations and palladium-catalysed cross-coupling reactions. Unusually for liquid crystals with bulky terminal chains, the smectic phase stability (particularly smectic C) is upheld by more than the nematic phase stability, and in most cases the smectic C phase stability is actually higher than comparable analogues with conventional unbranched terminal chains. It is postulated that the surprisingly high smectic C phase stability results from a phase separation effect due to the incompatibility of the spherical bulky group and the conventional unbranched terminal chain, hence implying that the smectic ‘layers’ are well defined, and such definition of the layers bodes well for bookshelf geometry in ferroelectric mixtures.     

Lipase-Catalyzed Acidolysis of Palm Mid Fraction Oil with Palmitic and Stearic Fatty Acid Mixture for Production of Cocoa Butter Equivalent

Cocoa butter equivalent (CBE) was prepared by enzymatic acidolysis reaction of substrate consisting of refined palm mid fraction oil and palmitic–stearic fatty acid mixture. The reactions were performed in a batch reactor at a temperature of 60 °C in an orbital shaker operated at 160 RPM. Different mass ratios of substrates were explored, and the composition of the five major triacylglycerols (TAGs) of the structured lipids was identified and quantified using cocoa butter certified reference material IRMM-801. The reaction resulted in production of cocoa butter equivalent with the TAGs' composition (1,3-dipalmitoyl-2-oleoyl-glycerol 30.7 %, 1-palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol 40.1%, 1-palmitoy-2,3- dioleoyl glycerol 9.0 %, 1,3-distearoyl-2-oleoyl-glycerol 14.5 %, and 1-stearoyl-2,3-dioleoyl glycerol 5.7 %) and with onset melting temperature of 31.6 °C and peak temperature of 40.4 °C which are close to those of cocoa butter. The proposed kinetics model for the acidolysis reaction presented the experimental data very well. The results of this research showed that palm mid fraction oil TAGs could be restructured to produce value added product such as CBE.     

In Silico and Experimental Characterization of Chimeric Bacillus thermocatenulatus Lipase with the Complete Conserved Pentapeptide of Candida rugosa Lipase

Lipases are one of the highest value commercial enzymes as they have broad applications in detergent, food, pharmaceutical, and dairy industries. To provide chimeric Bacillus thermocatenulatus lipase (BTL2), the completely conserved pentapeptide (¹¹²Ala-His-Ser-Gln-Gly¹¹⁶) was replaced with similar sequences (²⁰⁷Gly-Glu-Ser-Ala-Gly²¹¹) of Candida rugosa lipase (CLR) at the nucleophilic elbow region. For this purpose, three mutations including A112G, H113E, and Q115A were inserted in the conserved pentapeptide sequence of btl2 gene. Based on the crystal structures of 2W22, the best structure of opened form of the chimeric lipases were garnered using the MODELLER v9.10 software. The native and chimeric lipases were docked to a set of ligands, and a trial version of Molegro Virtual Docker (MVD) software was used to obtain the energy values. Docking results confirmed chimeric lipase to be better than the native lipase. Following the in silico study, cloning experiments were conducted and expression of native and chimeric btl2 gene in Pichia pastoris was performed. The native and chimeric lipases were purified, and the effect of these mutations on characteristics of chimeric lipase studied and then compared with those of native lipase. Chimeric lipase exhibited 1.6-fold higher activity than the native lipase at 55 °C. The highest percentage of both lipases activity was observed at 60 °C and pH of 8.0. The ion Ca²⁺ slightly inhibited the activity of both lipases, whereas the organic solvent enhanced the lipase stability of chimeric lipase as compared with the native lipase. According to the results, the presence of two glycine residues at the conserved pentapeptide region of this chimeric lipase (¹¹² Gly-Glu-Ser-Ala-Gly ¹¹⁶) may increase the flexibility of the nucleophilic elbow region and affect the enzyme activity level.     

Selective O-deallylation of dihydropyrazoles by molecular iodine in the presence of active N-allyl and formyl groups

Selective O-deallylation of dihydropyrazoles has been achieved by use of iodine (10 mol%) in PEG-400 as ecofriendly solvent. Iodine (10 mol%) in dimethyl sulfoxide at 100 °C also afforded O-deallylation with aromatization compatible with highly reactive N-allyl and formyl groups. The function of iodine in the synthesis of substituted pyrazoles under different conditions is described.     

Glabridin,a Stable Flavonoid of Glycyrrhiza glabra: HPTLC Analysis of the Traditional Formulation

JPC – Journal of Planar Chromatography – Modern TLC - A novel HPTLC method has been developed for the estimation of glabridin in Licorice rhizome and its Unani polyherbal formulation...     

Mechanism of structure formation of microbial cellulose during nascent stage

The structure of microbial cellulose (MC) produced by Acetobacter xylinum was studied in presence of Fluorescent Brightener, Direct Blue 1, 14, 15, 53, Direct Red 28, 75 and 79, as probe. X-ray diffraction pattern of the product showed that it was a crystalline complex of dye and cellulose. The product has the structure in which the monomolecular layer of the dye molecule is included between the cellulose sheets corresponding to the ( $ 1\bar{1}0 $ ) planes of microbial cellulose. As a result of dye inclusion, d-spacing of lower angle plane (100) of products becomes 8.0–8.8 Å instead of 6.1 Å of MC. The d-spacing for the higher angle plane must be (010) plane due to stronger van der Waals forces between the pyranose rings which reduced 5.3 Å space of (110) plane of MC to 3.9–4.5 Å in the product. However, cellulose regenerated from FB, DR28 products was cellulose I and IV, respectively, and that from each DB1, 14, 15, 53, DR75 and 79 products was cellulose II. Solid state ¹³C NMR and deuteration-IR showed the product was non-crystalline which was contrasted to X-ray results. The regenerated celluloses were cellulose I_β, IV_I and II, respectively. Thus the structure of the product depends on the characteristics of dye which affects the conformation of cellulose at the nascent stage by the direct interaction with cellulose chains. The different regenerated celluloses as well as different fine structure in the same cellulose allomorph were produced depending mainly on number and position of the sulfonate groups in the dye.     

Improved methods for the synthesis and isolation of imidazolium based ionic salts

Solvent-free reactions were used for the synthesis of a series of imidazolium-based ionic salts: 3,3′-[pyridine-2,6-diylbis(methylene)]bis(1-R-1H-imidazol-3-ium)chloride; (R = methyl, ethyl, butyl, isobutyl, hexyl, and benzyl). A simple and effective filtration process was used to isolate all the products in high purity and with yields ?93% within a 24 h period. The highly pure ionic compounds which are precursors to N-heterocyclic carbene ligands used in catalysis were fully characterized as gray-white hygroscopic salts.     

A catalyst-free protocol for direct oxidative esterification of alcohols and aldehydes

A fast, simple, and efficient protocol for the direct conversion of alcohols and aldehydes to methyl ester has been developed using TsNBr₂ without any catalyst. The one pot reaction proceeds in the presence of a base at room temperature in methanol, to produce the corresponding methyl ester in high yield within a short time.     

Synthesis of enantiopure furo[2,3-b]pyrroles

A simple method for the preparation of enantiopure furo[2,3-b]pyrroles, a rare class of concave bicyclic nitrogen and oxygen heterocycle, in promising yield has been developed. The 3-substituted pyrrolidinediones prepared from (2S,3S)-tetrahydro-3-hydroxy-5-oxo-2,3-furandicarboxylic acid (Garcinia acid) have been cyclized diastereo as well as enantioselectively to furo[2,3-b]pyrroles. The cyclization follows Baldwin’s rule.