Effect of enzymatic de-esterification and RG-I degradation of high methoxyl pectin (HMP) on sugar-acid gel properties.

The influence of RG-I domains on high methoxyl pectin (HMP) sugar-acid gel properties has rarely been reported. In our work, HMP was modified by enzymatic de-esterification and degradation of RG-I domains to compare and analyze the relationship between the structure and final sugar-acid gel properties. The results showed that the degree of esterification (DE) of REP (pectin degraded by rhamnosidase) and GEP (pectin debranched by galactosidase) was the same as that of untreated HMP, whereas the DE of PMEP (pectin de-esterified by pectin methyl esterase) decreased from 59.63 % to 54.69 %. The monosaccharide composition suggested no significant changes in the HG and RG-I structural domains of PMEP. In contrast, the percentage of RG-I structural domains of REP and GEP dropped from 37 % to about 28 %, accompanied by a reduction in the proportion of the RG-I backbones and side chains. The rheological characterization of sugar-acid gels demonstrated an enhanced gel grade for PMEP and a weakened one for REP and GEP. Moreover, we constructed a correlation relationship between the fine structure of pectin and the properties of the sugar-acid gels, confirming the critical contribution of the RG-I region (especially the neutral sugar side chains) to the HMP sugar-acid gels.

Characterization of Palm Fatty Acid Distillate, Diacylglycerol Regioisomers, and Esterification Products Using High-Performance Size Exclusion Chromatography.

High-performance size exclusion chromatography (HPSEC) equipped with an evaporative light scattering detector (ELSD) was utilized for characterization of palm fatty acid distillate (PFAD) and its esterified products, with a particular focus on lipid profiles and diacylglycerol (DAG) regioisomers. The separation of triacylglycerol (TAG), DAG, monoacylglycerol (MAG), and free fatty acid (FFA) was achieved through a single 100-Å Phenogel column, coupled with a 2-cm C18 guard, utilizing toluene/acetic acid (100:0.25, v/v) as the mobile phase. This separation was based on size sieving principles and the interactions between the hydroxyl group(s) and the Phenogel matrix. The limit of detection (LOD) and limit of quantification (LOQ) for the esterified PFAD products analyzed by this method fell within the range of 4.8-5.5 µg/mL and 14.7-16.7 µg/mL, respectively. Additionally, the same column, paired with a 2-cm silica guard and a mobile phase comprised of toluene/isooctane/acetic acid (35:65:0.15, v/v/v), was used for the characterization of DAG regioisomers within the esterified PFAD. LODs and LOQs for sn-1,3-DAG and sn- 1,2-DAG were determined to be 39.2 and 118.7 µg/mL, and 32.8 and 99.5 µg/mL, respectively. Investigation of esterified PFAD products prepared using 4% H2SO4 at 120°C. After 2 h, the analysis revealed the highest MAG content at 31.85%, accompanied by 51.54% DAG, 2.35% TAG, and a residual 14.27% FFA. Notably, as the reaction time extended, the MAG content decreased, while both DAG and TAG levels exhibited an increasing trend. Further examination of DAG regioisomers during PFAD esterification, under varying catalyst concentrations (2-10%) and reaction temperatures (80-140°C), demonstrated a significant increase in the percentage of sn-1,3-DAG, inversely correlated with the reduction in FFA from 2% H 2 SO 4 and 80°C onwards. Remarkably, the percentage of sn-1,2-DAG remained relatively stable regardless of changes in catalyst concentrations or temperatures, confirming its susceptibility to isomerization into the thermodynamically more stable sn-1,3-DAG form. This study provides valuable insights into the composition and behavior of esterified PFAD products.

Effects of pectin methyl-esterification on intestinal microbiota and its immunomodulatory properties in naive mice.

Pectins are dietary fibers that are attributed with several beneficial immunomodulatory effects. Depending on the degree of esterification (DE), pectins can be classified as high methoxyl pectin (HMP) or low methoxyl pectin (LMP). The aim of this study was to investigate the effects of pectin methyl-esterification on intestinal microbiota and its immunomodulatory properties in naive mice. Supplementation of the diet with LMP or HMP induced changes in the composition of the intestinal microbiota in mice toward Bacteroides, which was mainly promoted by HMP. Metabolome analysis of stool samples from pectin-fed mice showed a different effect of the two types of pectin on the levels of short-chain fatty acids and bile acids, which was consistent with highly efficient in vivo fermentation of LMP. Analysis of serum antibody levels showed a significant increase in IgG and IgA levels by both pectins, while FACS analysis revealed a decrease of infiltrating inflammatory cells in the intestinal lamina propria by HMP. Our study revealed that the structural properties of the investigated pectins determine fermentability, effects on microbial composition, metabolite production, and modulation of immune responses. Consumption of HMP preferentially altered the gut microbiota and suppressed pro-inflammatory immune responses, suggesting a beneficial role in inflammatory diseases.

Octadecyl and sulfonyl modification of diatomite synergistically improved the immobilization efficiency of lipase and its application in the synthesis of pine sterol esters.

Phytosterols usually have to be esterified to various phytosterol esters to avoid their disadvantages of unsatisfactory solubility and low bioavailability. The enzymatic synthesis of phytosterol esters in a solvent-free system has advantages in terms of environmental friendliness, sustainability, and selectivity. However, the limitation of the low stability and recyclability of the lipase in the solvent-free system, which often requires a relatively high temperature to induce the viscosity, also increased the industrial production cost. In this context, a low-cost material, namely diatomite, was employed as the support in the immobilization of Candida rugosa lipase (CRL) due to its multiple modification sites. The Fe3 O4 was also then introduced to this system for quick and simple separation via the magnetic field. Moreover, to further enhance the immobilization efficiency of diatomite, a modification strategy which involved the octadecyl and sulfonyl group for regulating the hydrophobicity and interaction between the support and lipase was successfully developed. The optimization of the ratio of the modifiers suggested that the -SO3 H/C18 (1:1.5) performed best with an enzyme loading and enzyme activity of 84.8 mg·g-1 and 54 U·g-1 , respectively. Compared with free CRL, the thermal and storage stability of CRL@OSMD was significantly improved, which lays the foundation for the catalytic synthesis of phytosterol esters in solvent-free systems. Fortunately, a yield of 95.0% was achieved after optimizing the reaction conditions, and a yield of 70.0% can still be maintained after six cycles.

Extending the computational and experimental analysis of lipase active site selectivity.

Molecular docking is an important computational analysis widely used to predict the interaction of enzymes with several starting materials for developing new valuable products from several starting materials, including oils and fats. In the present study, molecular docking was used as an efficient in silico screening tool to select biocatalysts with the highest catalytic performance in butyl esters production in a solvent-free system, an eco-friendly approach, via direct esterification of free fatty acids from Licuri oil with butanol. For such purpose, three commercial lipase preparations were used to perform molecular docking studies such as Burkholderia cepacia (BCL), Porcine pancreatic (PPL), and Candida rugosa (CRL). Concurrently, the results obtained in BCL and CRL are the most efficient in the esterification process due to their higher preference for catalyzing the esterification of lauric acid, the main fatty acid found in the licuri oil composition. Meanwhile, PPL was the least efficient because it preferentially interacts with minor fatty acids. Molecular docking with the experimental results indicated the better performance in the synthesis of esters was BCL. In conclusion, experimental results analysis shows higher enzymatic productivity in esterification reactions of 1294.83 µmol/h.mg, while the CRL and PPL demonstrated the lowest performance (189.87 µmol / h.mg and 23.96 µmol / h.mg, respectively). Thus, molecular docking and experimental results indicate that BCL is a more efficient lipase to produce fatty acids and esters from licuri oil with a high content of lauric acid. In addition, this study also demonstrates the application of molecular docking as an important tool for lipase screening to achieve more sustainable production of butyl esters with a view synthesis of biolubricants.

Comparison of soluble dietary fibers from various quinoa microgreens: Structural characteristics and bioactive properties.

Quinoa (Chenopodium quinoa Willd.) microgreens are widely consumed as healthy vegetables around the world. Although soluble dietary fibers exist as the major bioactive macromolecules in quinoa microgreens, their structural characteristics and bioactive properties are still unclear. Therefore, the structural characteristics and bioactive properties of soluble dietary fibers from various quinoa microgreens (QMSDFs) were investigated in this study. The yields of QMSDFs ranged from 38.82 to 52.31 mg/g. Indeed, all QMSDFs were predominantly consisted of complex pectic-polysaccharides, e.g., homogalacturonan (HG) and rhamnogalacturonan I (RG I) pectic domains, with the molecular weights ranged from 2.405 × 104 to 5.538 × 104 Da. In addition, the proportions between RG I and HG pectic domains in all QMSDFs were estimated in the range of 1: 2.34-1: 4.73 (ratio of galacturonic acid/rhamnose). Furthermore, all QMSDFs exhibited marked in vitro antioxidant, antiglycation, prebiotic, and immunoregulatory effects, which may be partially correlated to their low molecular weights and low esterification degrees. These findings are helpful for revealing the structural and biological properties of QMSDFs, which can offer some new insights into further development of quinoa microgreens and related QMSDFs as value-added healthy products.

Production of biodiesel from waste fish fat through ultrasound-assisted transesterification using petro-diesel as cosolvent and optimization of process parameters using response surface methodology.

Biodiesel is a highly promising and viable alternative to fossil-based diesel that also addresses the urgent need for effective waste management. It can be synthesized by the chemical modification of triglycerides sourced from vegetable origin, animal fat, or algal oil. The transesterification reaction is the preferred method of producing biodiesel. However, the non-miscibility of alcohol and oil layer causes excessive utilization of alcohol, catalyst, and a substantial reacting time and temperature. In the current investigation, transesterification of waste fish oil was performed with petro-diesel as cosolvent, under the influence of ultrasound energy. The combination of both techniques is a unique and efficient way to minimize the mass transfer limitations considerably and hence reduces the parameters of the reaction. It is also a sincere effort to comply with the principles of green chemistry. The optimum reaction conditions were obtained using response surface methodology (RSM) that were as follows: molar ratio of methanol to oil 9.09:1, catalyst concentration of 0.97 wt%, cosolvent concentration of 29.1 wt%, temperature 60.1℃, and a reacting time 30 min. Under these listed conditions, 98.1% biodiesel was achievable, which was in close agreement with the expected result. In addition, the cosolvent removal step from the crude biodiesel was also eliminated as it could be employed as a blended fuel in CI engines.

Enhancing biocatalyst performance through immobilization of lipase (Eversa® Transform 2.0) on hybrid amine-epoxy core-shell magnetic nanoparticles.

Magnetic nanoparticles were functionalized with polyethylenimine (PEI) and activated with epoxy. This support was used to immobilize Lipase (Eversa® Transform 2.0) (EVS), optimization using the Taguchi method. XRF, SEM, TEM, XRD, FTIR, TGA, and VSM performed the characterizations. The optimal conditions were immobilization yield (I.Y.) of 95.04 ± 0.79 %, time of 15 h, ionic load of 95 mM, protein load of 5 mg/g, and temperature of 25 °C. The maximum loading capacity was 25 mg/g, and its stability in 60 days of storage showed a negligible loss of only 9.53 % of its activity. The biocatalyst demonstrated better stability at varying temperatures than free EVS, maintaining 28 % of its activity at 70 °C. It was feasible to esterify free fatty acids (FFA) from babassu oil with the best reaction of 97.91 % and ten cycles having an efficiency above 50 %. The esterification of produced biolubricant was confirmed by NMR, and it displayed kinematic viscosity and density of 6.052 mm2/s and 0.832 g/cm3, respectively, at 40 °C. The in-silico study showed a binding affinity of -5.8 kcal/mol between EVS and oleic acid, suggesting a stable substrate-lipase combination suitable for esterification.

Biodiesel production and exploring properties of Datura stramonium L. oil with its optimization using combined approaches-Taguchi, grey relational analysis, and response surface methodology.

Biodiesel production through the synthesis of Datura stramonium L. oil is studied to explore the most efficient approaches to suggest an alternate feedstock for biodiesel production. The main objective of this work is to optimize the process variables of biodiesel synthesis by using some statistical approach (Taguchi method, grey relational analysis (GRA), and response surface methodology (RSM) analyzing three parameters, i.e., alcohol-to-oil molar ratio, catalyst (NaOH) concentration, and process temperature for achieving maximum biodiesel derived from Datura stramonium L. oil. The transesterification process is applied by using an ultrasonic-assisted technique. Grey relational analysis (GRA) was successfully applied with the Taguchi method resulting in the optimum combination of A2B1C1. Based on the findings, the best operating conditions for transesterifying are attained with the RSM approach consisting of a 5.697:1 molar ratio (level 2), 0.3 (wt.%) NaOH concentration (level 1), and 70 °C process temperature (level 1). With a value of 87.02%, these ideal operating conditions produce the maximum yield as compared to grey relational analysis (GRA) yields 83.99%. The obtained results have been verified through the characterization of oil and biodiesel as well. Also, the fuel qualities of DSL biodiesel were identified and assessed. DSL oil was found 137.6 degrees of unsaturation during fatty acid profile analysis. DSL biodiesel was found the best kinematic viscosity (4.2 mm2/s) and acid value (0.49) when compared to Karanja and palm biodiesel. D. stramonium L. was recognized as a suitable species for biodiesel feedstock according to the findings.

Measuring risk of renewable diesel production processes using a multi-criteria decision strategy.

This study proposes measuring the risk of five alternative renewable diesel production technologies using a multi-criteria decision matrix strategy. Evaluated criteria include environmental, economic, technological, social, and process safety risks. The subjective Analytical Hierarchy Process (AHP) with stakeholder input provides criteria and sub-criteria weightings and the Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS) ranks alternatives. Alternative renewable diesel options are Green Diesel from first, second, and third-generation feedstocks, Fischer-Tropsch Diesel from second-generation biomass, and the transesterification of vegetable oils (VO) to make biodiesel. This study is a response to an earlier work measuring the sustainability of the same renewable technologies. While the previous work indicated Fischer-Tropsch Diesel as the most sustainable, this current work indicated the process as the "most risky," suggesting that risk is a significant driver of decision making over sustainability, and newly developed decision tools should address both perspectives.

Comparison on emulsifying and emulgelling properties of low methoxyl pectin with varied degree of methoxylation from different de-esterification methods.

Low methoxyl pectin (LMP) with different degree of methoxylation (DM, 40-50 %, 20-30 % and 5-10 %) were prepared from commercially available citrus pectin using high hydrostatic pressure assisted enzymatic (HHP-pectin) and traditional alkaline (A-pectin) de-esterification method. The results showed that both de-esterification methods and DM exhibited LMPs with varied physicochemical, structural, and functional properties. As the DM decreased, LMP showed a decrease in molecular weight (Mw), while an increase in negative charges and rhamnogalacturonan I (RG-I) ratio, accompanied with better emulsion stability, emulsion gel strength and water-holding properties. Relative to A-pectin, HHP-pectin had higher Mw and lower RG-I side chain ratio, contributing to its better thermal stability, apparent viscosity, and emulgelling properties. HHP-pectin with lower DM (5-10 %) showed superior thickening, emulsifying and emulgelling properties, while that with higher DM (40-45 %) had superior thermal stability, which provided alternative for de-esterification and targeted structural modification of pectin.

Kj-mhpC Enzyme in Klebsiella jilinsis 2N3 Is Involved in the Degradation of Chlorimuron-Ethyl via De-Esterification.

Microbial degradation is a highly efficient and reliable approach for mitigating the contamination of sulfonylurea herbicides, such as chlorimuron-ethyl, in soil and water. In this study, we aimed to assess whether Kj-mhpC plays a pivotal role in the degradation of chlorimuron-ethyl. Kj-mhpC enzyme purified via prokaryotic expression exhibited the highest catalytic activity for chlorimuron-ethyl at 35 °C and pH 7. Bioinformatic analysis and three-dimensional homologous modeling of Kj-mhpC were conducted. Additionally, the presence of Mg+ and Cu2+ ions partially inhibited but Pb2+ ions completely inhibited the enzymatic activity of Kj-mhpC. LC/MS revealed that Kj-mhpC hydrolyzes the ester bond of chlorimuron-ethyl, resulting in the formation of 2-(4-chloro-6-methoxypyrimidine-2-amidoformamidesulfonyl) benzoic acid. Furthermore, the point mutation of serine at position 67 (Ser67) confirmed that it is the key amino acid at the active site for degrading chlorimuron-ethyl. This study enhanced the understanding of how chlorimuron-ethyl is degraded by microorganisms and provided a reference for bioremediation of the environment polluted with chlorimuron-ethyl.

Improved biocatalytic activity of steapsin lipase in supercritical carbon dioxide medium for the synthesis of benzyl butyrate: A commercially important flavour compound.

Enzymatic synthesis of flavours, fragrances and food additives compounds have great demand and market value. Benzyl butyrate is commercially important flavour and food additive compound having global use around 100 metric tons/year and widely used in various industrial sectors. However, industrial synthesis of food additive benzyl butyrate is carried out by conventional chemical process which demands for the green biobased sustainable synthetic process. The present work reports steapsin catalyzed synthesis of benzyl butyrate for the first time in supercritical carbon dioxide (Sc-CO2) reaction medium. All reaction variables are optimized in details to obtain competent conversion of 99% in Sc-CO2 reaction medium. The developed steapsin catalyzed synthesis in Sc-CO2 medium offered almost four-fold higher conversion to benzyl butyrate than organic (conventional) solvent. The steapsin biocatalyst was effectually recycled up to five reaction cycles in Sc-CO2 medium. Moreover, the developed steapsin catalyzed protocol in Sc-CO2 medium was extended to synthesize different ten industrially significant flavour fragrance compounds that offers 99% conversion and three to five-folds higher conversion than organic medium. Thus, the present steapsin catalyzed protocol offered improved synthesis of various commercially significant flavour compounds in Sc-CO2. medium.

Amino acid application inhibits root-to-shoot cadmium translocation in Chinese cabbage by modulating pectin methyl-esterification.

The exogenous application of amino acids (AAs) generally alleviates cadmium (Cd) toxicity in plants by altering their subcellular distribution. However, the physiological mechanisms underlying AA-mediated cell wall (CW) sequestration of Cd in Chinese cabbage remain unclear. Using two genotypes of Chinses cabbage, Jingcui 60 (Cd-tolerant) and 16-7 (Cd-sensitive), we characterized the root structure, subcellular distribution of Cd, CW component, and related gene expression under the Cd stress. Cysteine (Cys) supplementation led to a reduction in the Cd concentration in the shoots of Jingcui 60 and 16-7 by 65.09 % and 64.03 %, respectively. Addition of Cys alleviated leaf chlorosis in both cultivars by increasing Cd chelation in the root CW and reducing its distribution in the cytoplasm and organelles. We further demonstrated that Cys supplementation mediated the downregulation of PMEI1 expression and improving the activity of pectin methyl-esterase (PME) by 17.98 % and 25.52 % in both cultivars, respectively, compared to the Cd treatment, resulting in an approximate 12.00 %-14.70 % increase in Cd retention in pectin. In contrast, threonine (Thr) application did not significantly alter Cd distribution in the shoots of either cultivar. Taken together, our results suggest that Cys application reduces Cd root-to-shoot translocation by increasing Cd sequestration in the root CW through the downregulation of pectin methyl-esterification.

Insight into the Feasibility of Fatty Acyl Chlorides with 10-18 Carbons for the Ball-Milling Synthesis of Thermoplastic Cellulose Esters.

Fatty acid cellulose esters (FACE) are common cellulose-based thermoplastics, and their thermoplasticity is determined by both the contents and the lengths of the side chains. Herein, various FACE were synthesized by the ball-milling esterification of cellulose and fatty acyl chlorides containing 10-18 carbons, and their structures and thermoplasticity were thoroughly studied. The results showed that FACE with high degrees of substitution (DS) and low melting flow temperatures (Tf) were achieved as the chain lengths of the fatty acyl chlorides were reduced. In particular, a cellulose decanoate with a DS of 1.85 and a Tf of 186 °C was achieved by feeding 3 mol of decanoyl chloride per mole anhydroglucose units of cellulose. However, cellulose stearate (DS = 1.53) synthesized by the same protocols cannot melt even at 250 °C. More interestingly, the fatty acyl chlorides with 10 and 12 carbons resulted in FACE with superior toughness (elongation at break up to 94.4%). In contrast, due to their potential crystallization of the fatty acyl groups with 14-18 carbons, the corresponding FACE showed higher tensile strength and Young's modulus than the others. This study provides some theoretical basis for the mechanochemical synthesis of thermoplastic FACE with designated properties.

Batch and continuous enzymatic interesterification of beef tallow: Interesterification degree, reaction relationship, and physicochemical properties.

The relationship between batch and continuous enzymatic interesterification was studied through enzymatic interesterification of beef tallow. The interesterification degree (ID) during the batch reaction was monitored based on triacylglycerol composition, sn-2 fatty acid composition, solid fat content, and melting profile and was described by an exponential model. A relationship equation featuring reaction parameters of the two reations was established to predict the ID and physicochemical characteristics in continuous interesterification. The prediction of the ID based on triacylglycerol composition was reliable, with an R2 value greater than 0.85. Interesterification produced more high-melting-point components for both reactions, but the acyl migration in the batch-stirring reactor was much greater, resulting in faster crystallization, a more delicate crystal network, and lower hardness. The relationship equation can be employed to predict the ID, but the prediction of physicochemical properties was constrained by the difference in acyl migration degree between the two reactions.

Optimizing the enzymatic production of biolubricants by the Taguchi method: Esterification of the free fatty acids from castor oil with 2-ethyl-1-hexanol catalyzed by Eversa Transform 2.0.

The solvent-free esterification of the free fatty acids (FFAs) obtained by the hydrolysis of castor oil (a non-edible vegetable oil) with 2-ethyl-1-hexanol (a branched fatty alcohol) was catalyzed by different free lipases. Eversa Transform 2.0 (ETL) features surpassed most commercial lipases. Some process parameters were optimized by the Taguchi method (L16'). As a result, a conversion over 95% of the FFAs of castor oil into esters with lubricants properties was achieved under optimized reaction conditions (15 wt% of biocatalyst content, 1:4 molar ratio (FFAs/alcohol), 30 °C, 180 rpm, 96 h). The substrates molar ratio had the highest influence on the dependent variable (conversion at 24 h). FFAs/2-ethyl-1-hexanol esters were characterized regarding the physicochemical and tribological properties. Interestingly, the modification of the FFAs with 2-ethyl-1-hexanol by ETL increased the oxidative stability of the FFAs feedstock from 0.18 h to 16.83 h. The biolubricants presented a lower friction coefficient than the reference commercial mineral lubricant (0.052 ± 0.07 against 0.078 ± 0.04). Under these conditions, ETL catalyzed the oligomerization of ricinoleic acid (a hydroxyl fatty acid) into estolides, reaching a conversion of 25.15% of the initial FFAs (for the first time).

PNPLA1 knockdown inhibits esterification of γ-linolenic acid to ceramide 1 in differentiated keratinocytes.

Patatin-like phospholipase domain-containing 1 (PNPLA1) is crucial in the esterification of linoleic acid (LA; 18:2n-6) to ω-hydroxy fatty acids (FA) of ceramide 1 (Cer1), the major barrier lipid of the differentiated epidermis. We previously reported that γ-linolenic acid (GLA; 18:3n-6) as well as LA is esterified to Cer1 subspecies with sphingosine (d18:1) or eicosasphingosine (d20:1) amide-linked to two different ω-hydroxy FA (30wh:0; 32wh:1). Here, we further investigated whether PNPLA1 is also responsible for esterification of GLA to these Cer1 subspecies in normal human keratinocytes (NHK). As late/terminal differentiation was induced in NHK, PNPLA1 and differentiation markers were expressed, and LA-esterified Cer1 subspecies (18:2n-6/C30wh:0 or C32wh:0/d18:1; 18:2n-6/C32wh:0/d20:1) were detected, which were further increased with LA treatment. GLA-esterified Cer1 subspecies (18:3n-6/C30wh:0 or C32wh:0/d18:1; 18:3n-6/C32wh:0/d20:1) were detected only with GLA treatment. Specific small interfering RNA-mediated knockdown of PNPLA1 (KDP) in differentiated NHK decreased levels of these LA-esterified Cer1 subspecies overall and of involucrin (IVL), a terminal differentiation marker. Moreover, KDP resulted in lesser LA/GLA responses as characterized by more significant decreases in IVL and LA/GLA-esterified Cer1 subspecies overall and an accumulation of non-esterified ω-hydroxy ceramides, their putative precursors; the decrease of 18:3n-6/C32wh:0/d18:1, the predominant GLA-esterified Cer1 subspecies, specifically paralleled the increase of C32wh:0/d18:1, its corresponding precursor. PNPLA1 is responsible for NHK terminal differentiation and also for esterification of GLA to the ω-hydroxy FA of Cer1.

Synthesis and antimicrobial studies of cadasides analogues via on-resin esterification.

A series of cadasides analogues have been prepared via a combination of solid-phase peptide synthesis and solution-phase cyclization. Primary structure-activity relationship studies of cadasides have also been established and revealed the critical roles of unnatural amino acid residues, which will facilitate the further development of cadasides analogues with improved antimicrobial activities.

Solvent-free synthesis of hydrophobic and amphiphilic esters using a chemically modified lipase from Thermomyces lanuginosus: a comparative study with native and immobilized forms.

Using lipases to catalyze the synthesis of the most differentiated type of compounds remains one of the major challenges among scientists. Seeking more economic and advantageous catalysts is a current goal of green chemistry. In this work, we demonstrate the potential of a chemically modified form of lipase from Thermomyces lanuginosus (cmLTL) for the synthesis of both hydrophobic (heptyl heptanoate, heptyl octanoate, heptyl decanoate, decyl heptanoate, decyl octanoate and decyl decanoate) and amphiphilic (2-(2-ethoxyethoxy)ethyl oleate and 2-(2-ethoxyethoxy)ethyl linoleate) esters, in bulk. The results were compared with its native (LTL) and immobilized (imLTL) forms. The data revealed that LTL showed poor activity for all reactions performed with n-heptane (η<20 %). ImLTL was able to synthesize all hydrophobic esters (η>60 %), with exception of the short ester, heptyl heptanoate. cmLTL was the only form of LTL capable of producing hydrophobic and amphiphilic esters, without compromising the yield when the reactions were performed under solvent-free conditions (>50 %). Molecular modeling showed that the active pocket of cmLTL is able to deeply internalize transcutol, with stronger interactions, justifying the outstanding results obtained. Furthermore, owing to the possibility of cmLTL filtration, the reusability of the catalyst is ensured for at least 6 cycles, without compromising the reaction yields.