Synthesis of Hydrophilic Derivative Surfactants From Algae-Derived Unsaponifiable Lipids

In the context of decarbonizing the economy, the utilization of biologically sourced feedstocks to produce replacements for petroleum-derived materials is becoming more urgent. Improving renewable biomass production and utilization is imperative for commercializing future biorefineries. Algae-derived biomass is a particularly promising feedstock thanks to its attractive oil content and composition; specifically, the high-value products in the unsaponifiable lipids have not been included in a conversion process. Here we demonstrate surfactant synthesis from a complex oil fraction as the hydrophobic donor moieties, yielding products that are similar to commercially available surfactants such as the linear alkyl benzene sulfonates. Unsaponifiable lipids extracted from algae were derivatized to non-ionic surfactants using a green chemical synthesis route based on a double esterification with succinic acid and polyethylene glycol. The in-depth molecular and structural surfactant characterization is included and indicates that the resulting properties fall between those of pure cholesterol and phytol used as surrogates for the reaction synthesis demonstration. This is the first demonstration of an effective and potentially high-value synthesis of functional surfactants with properties that can be tailored based on the relative composition of the resulting hydrocarbon alcohol components in the mixture. This novel green chemistry synthesis approach provides a route to high-value product synthesis from algae.

Isolation of guaiene from crude and distillate patchouli oil extracted by molecular distillation

Guaiene is one of the components of sesquiterpenes that affects the patchouli oil fragrance. It is commonly used in the pharmaceutical industry and is also used as a flavoring and fragrance agent in the food industry. The objective of this study was to obtain the highest content of guaiene and to investigate the effect of the isolation stage by the molecular distillation process. Crude and distillate fraction patchouli oil samples were introduced into the molecular distillation system. The process conditions applied were first-stage and second-stage molecular distillation. Parameters observed were in terms of chemical composition and color. Results obtained the highest content of a-guaiene in the patchouli oil fraction distillate provided by second-stage molecular distillation (23.53%). However, the highest content of A-guaiene was revealed in second-stage molecular distillation residues (33.15%) of patchouli oil fraction distillate samples. The chromaticity value of the second stage distillate was yellow while the residue was yellow-red, respectively.

SEPARATION OF OIL-WATER EMULSIONS

Статья посвящена исследованию разделения водонефтяных эмульсий. Большинство существующих месторождений находятся на завершающей стадии разработки, что характеризуется ростом обводненности добываемой нефтяной фракции. При наличии высокоустойчивых «застарелых» ловушечных нефтей для повышения эффективности и надежности процессов их обезвоживания используют методы разделения с применением деэмульгаторов. Наибольшее распространение, в настоящее время получили деэмульгаторы неионогенной природы. В работе была оценена эффективность трех деэмульгаторов, соответствующих государственным санитарно-эпидемиологическим правилам и нормативам: Эмалсатрон R2601-A, Химтехно-527, СНПХ-4114. Исследуемые деэмульгаторы успешно прошли испытания и могут быть рекомендованы к промышленному применению, так как обладают рядом преимуществ. The article is devoted to the study of the separation of oil-water emulsions. Most of the existing fields are at the final stage of development, which is characterized by an increase in the water content of the extracted oil fraction. In the presence of highly stable "old" trap oils, separation methods with the use of demulsifiers are used to increase the efficiency and reliability of their dewatering processes. The most widespread, at present, are demulsifiers of a non-ionic nature. The work evaluated the effectiveness of three demulsifiers that comply with state sanitary and epidemiological rules and regulations: Emalsatron R2601-A, Chemtechno-527, SNPH-4114. The studied demulsifiers have been successfully tested and can be recommended for industrial use, as they have a number of advantages.

Influence of Supercritical Carbon Dioxide Extraction Conditions on Extraction Yield and Composition of Nigella sativa L. Seed Oil—Modelling, Optimization and Extraction Kinetics regarding Fatty Acid and Thymoquinone Content

Nigella sativa L. is cultivated in many regions and its seeds have found use in variety of foods, but also in traditional medicine due to high content of biologically active essential oils. In this work optimization of supercritical carbon dioxide extraction from N. sativa seeds was performed using response surface methodology to describe the influence of extraction conditions on oil yield. Kinetics of oil and thymoquinone extraction were analyzed as well. It was demonstrated that in order to collect thymoquinone-rich N. sativa oil fraction, appropriate for health-related applications, the extraction should be carried out at 40 °C and 10–15 MPa. Following application of higher pressure of 35 MPa enables effective extraction of remaining oil rich in polyunsaturated fatty acids suitable for use in food industry. Thymoquinone-dependent antibacterial activity of the N. sativa seed oil was observed against bacterial pathogens: Haemophilus influenzae, Staphylococcus haemolyticus, Staphylococcus epidermidis, Enterococcus faecalis and Escherichia coli.

Hydrodesulfurization of 4,6-Dimethyldibenzothiophene and the Diesel Oil Fraction on NiMo Catalysts Supported over Proton-Exchanged AlMCM-41 and TiMCM-41 Extrudates

NiMo catalysts supported on mesoporous MCM-41 type materials shaped with binder were tested for activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DMDBT) and the diesel fuel fraction (0.92 wt% of sulfur). The aim of the investigation was to evaluate the effect of ion exchange with protons of Al- or Ti-substituted MCM-41 mesoporous supports. The subjected catalytic systems were NiMo/HAlMCM-41 and NiMo/HTiMCM-41, and for comparison purposes NiMo/AlMCM-41 and NiMo/TiMCM-41. The samples were characterized by N2 sorption (at 77 K), XRD, TEM, XPS, SEM and Py–IR. It was found that the functionalization of AlMCM-41 and TiMCM-41 with protons increased the conversion of 4,6-DMDBT and the pseudo-first-order rate constant. Correspondingly, 4,6-DMDBT HDS reactions over the NiMo/HTiMCM-41 catalyst proceeded to a similar extent via hydrogenation and direct desulfurization, whereas over the NiMo/HAlMCM-41 they proceeded mainly via direct desulfurization. Furthermore, the ion-exchanged catalysts displayed two-fold higher efficiency in direct desulfurization than their non-modified counterparts. The NiMo/HTiMCM-41 catalyst exhibited the highest catalytic efficiency in the HDS of 4,6-DMDBT and the diesel oil fraction. The high activity of the NiMo/HTiMCM-41 catalyst is mainly attributed to its appropriate acidity, as well as the metal–support interaction providing both the high dispersion of the active phase and the desirable multilayered stacking morphology of the active phase slabs.

RESEARCH OF FAT MIXTURES – ANALOGUES MID-FRACTION OF PALM OIL

Совершенствование процессов модификации масел и жиров при получении жировых полуфабрикатов с оптимальными свойствами кристаллообразования является актуальным для масложирового и кондитерского производств. Существует ограниченное количество природных растительных масел с оптимальным жирнокислотным и триглицеридным составом для применения в качестве основы жировых смесей при производстве кондитерских жировых начинок. Богатые насыщенными жирными кислотами какао-масло и масло ши являются дорогостоящими жировыми компонентами со специфическими свойствами для использования в кондитерских изделиях. Между тем пальмовое масло имеет хороший баланс между насыщенными и ненасыщенными жирными кислотами. С целью снижения себестоимости жировых полуфабрикатов за счет повторной переработки образующихся промежуточных олеиновых фракций пальмового масла и получения жировых полуфабрикатов, имеющих аналогичные средней фракции пальмового масла физико-химические и структурно-механические свойства, проведено комплексное исследование физико-химических свойств и основных показателей плавления и застывания разработанных жировых композиций: температура застывания не более 23,4°C; твердость при 20°C от 43,7 до 44,7%; массовая доля триглицерида POP от 41,4 до 42,7%. Физико-химические характеристики исходных компонентов жировых полуфабрикатов, %, твердость при 20°C: промежуточной олеиновой фракции 32,5; первой стеариновой фракции 74,3; средней фракции пальмового масла 45,6. Температура плавления промежуточной олеиновой фракции 32,8°C. Получены образцы жировых полуфабрикатов для производства кондитерских жировых начинок (индекс кристаллизации от 1,9 до 2,0). Результаты исследования показали возможность создания жировых полуфабрикатов – аналогов средней фракции пальмового масла, имеющих в составе 10% промежуточной олеиновой фракции. Improvement of the processes of modification of oils and fats when obtaining fatty semi-finished products with optimal crystal formation properties is relevant for production fat and oil products and confectionery. There is a limited amount of natural vegetable oils with an optimal fatty acid and triglyceride composition for use as the basis of fatty mixtures in the production of confectionery fat fillings. Rich in saturated fatty acids, cocoa butter and shea butter are expensive fatty components with specific properties for use in confectionery. Meanwhile, palm oil has a good balance between saturated and unsaturated fatty acids. In order to reduce the cost of semi-finished fat products by re-processing the formed intermediate oleic fractions of palm oil and obtaining fat semi-finished products having physicochemical and structural-mechanical properties similar to the middle fraction of palm oil, a comprehensive study of the physicochemical properties and the main indicators of melting and solidification developed fatty compositions: pour point no more than 23,4°C; hardness at 20°Cfrom 43,7 to 44,7%; mass fraction of POP triglyceride from 41,4 to 42,7%. Physical and chemical characteristics of the initial components of fatty semi-finished products, %, hardness at 20°C: intermediate oleic fraction 32,5; first stearic fraction 74,3; middle palm oil fraction 45,6. The melting point of the intermediate oleic fraction is 32,8°C. Samples of fatty semi-finished products for the production of confectionery fatty fillings (crystallization index from 1,9 to 2,0) were obtained. The results of the study showed the possibility of creating fatty semi-finished products – analogues of the mid-fraction of palm oil, which contain 10% of the intermediate oleic fraction.

Application of Proteomics and Metabonomics to Reveal the Molecular Basis of Atractylodis Macrocephalae Rhizome for Ameliorating Hypothyroidism Instead of Hyperthyroidism

As the treatments of diseases with Chinese herbs are holistic and characterized by multiple components, pathways, and targets, elucidating the efficacy of Chinese herbs in treating diseases, and their molecular basis, requires a comprehensive, network-based approach. In this study, we used a network pharmacology strategy, as well as in vivo proteomics and metabonomics, to reveal the molecular basis by which Atractylodis macrocephalae rhizome (AMR) ameliorates hypothyroidism. Eighteen main compounds from AMR and its fractions (volatile oil fraction, crude polysaccharides fraction, lactones fraction, oligosaccharide fraction, and atractyloside fraction) were identified by HPLC, and their targets were screened using the TCMSP database and Swiss Target Prediction. Disease targets were gathered from the TTD, CTD and TCMSP databases. Hub targets were screened by different plug-ins, such as Bisogene, Merge, and CytoNCA, in Cytoscape 3.7.1 software and analyzed for pathways by the DAVID database. Hypothyroidism and hyperthyroidism pharmacological models were established through systems pharmacology based on proteomic and metabolomic techniques. Finally, AMR and its fractions were able to ameliorate the hypothyroidism model to different degrees, whereas no significant improvements were noted in the hyperthyroidism model. The lactones fraction and the crude polysaccharides fraction were considered the most important components of AMR for ameliorating hypothyroidism. These amelioration effects were achieved through promoting substance and energy metabolism. In sum, the integrative approach used in this study demonstrates how network pharmacology, proteomics, and metabolomics can be used effectively to elucidate the efficacy, molecular basis, and mechanism of action of medicines used in TCM.

Experimental and computational studies of an antiplasmodial derivative of allantoin; antimycobacterial essential oil from Cordia batesii WERNHAM (Boraginaceae)

Background Chemical and pharmacological investigations were performed on the stems of Cordia batesii (Boraginaeae); chemical studies included quantum calculations applied on a newly described compound. Results A new derivative of allantoin (1) named batesiin (2) was characterized. Thirteen other known compounds involving allantoin (1) were either isolated or identified. GC–MS enabled the identification of six compounds from a fraction containing essential oil. MeOH extract and some isolated compounds were tested in vitro against Pf7G8 CQS and Pf Dd2 CQR strains of Plasmodium falciparum; extract disclosed a moderate antiplasmodial activity (IC50 = 50 μg mL−1). Meantime, the CH2Cl2 extract and essential oil fraction were tested on a resistant mycobacterial strain of Mycobacterium tuberculosis; a potent antimycobacterial activity with a MIC = 9.52 μg mL−1 was deduced from essential oil. Density functional theory (DFT) calculations were carried on batesiin (2). Calculated chemical shifts at B3LYP/6-31G(d,p) and MPW1PW91/6-31G+(d,p) showed much better correlations with the experimental data. Time dependent DFT at B3LYP/6-31G+(d,p) displayed a major absorption band 3.01 nm higher than the experimental value. Conclusion Cordia batesii can be considered as promising in search of compounds with antimalarial and antitubercular properties. DFT studies are very helpful when trying to learn more about the spectroscopic insights of a derivative of allantoin (1).