Acylamino Acids Research Articles

Ion-Specific Effects on Vesicle-to-Micelle Transitions of an Amino Acid Surfactant Probed by Chemical Trapping.

Ion-specific effects widely exist in biological and chemical systems and cannot be explained by classical theories. The complexity of ion-specific effects in protein systems at the molecular level necessitates the use of mimetic models involving smaller molecules, such as amino acids, oligopeptides, and other organic molecules bearing amide bonds. Therefore, it is of theoretical value to determine the effect of additional salts on the aggregation transitions of acyl amino acid surfactants. Herein, the effects of specific tetraalkylammonium ions (TAA+) on sodium lauroyl glycinate (SLG) aggregation were studied by dynamic light scattering (DLS) and transmission electron microscopy. Although previous studies have shown that the kosmotropic TAA+ ions tend to induce micellar growth or micelle-to-vesicle transitions of some anionic surfactants, TAA+ addition in the present study induced partial vesicle-to-micelle transitions in SLG solutions. The chemical trapping (CT) method was employed to estimate changes in the interfacial molarities of water, amide bonds, and carboxylate groups during such transitions. The vesicle-to-micelle transitions were accompanied by a marked rise in interfacial water molarity and a decline in interfacial amide bonds molarity, suggesting that the hydrated TAA+ entered the interfacial region and disrupted hydrogen bonding, thus preventing the SLG monomers from packing tightly. Molecular dynamic simulation was also performed to demonstrate the salt-induced cleavage of amide-amide bonds between SLG headgroups. Furthermore, both CT and DLS results show that the ability of tetraalkylammonium cations to induce such transitions increased with increasing size and hydrophobicity of the cation, which follows the Hofmeister series. The current study offers critical molecular-level evidence for understanding the specific effects of tetraalkylammonium ions on the aggregation transitions of an acyl amino acid surfactant.

Establishing the potency of N-acyl amino acids versus conventional fatty acids as thermogenic uncouplers in cells and mitochondria from different tissues.

The possibility that N-acyl amino acids could function as brown or brite/beige adipose tissue-derived lipokines that could induce UCP1-independent thermogenesis by uncoupling mitochondrial respiration in several peripheral tissues is of significant physiological interest. To quantify the potency of N-acyl amino acids versus conventional fatty acids as thermogenic inducers, we have examined the affinity and efficacy of two pairs of such compounds: oleate versus N-oleoyl-leucine and arachidonate versus N-arachidonoyl-glycine in cells and mitochondria from different tissues. We found that in cultures of the muscle-derived L6 cell line, as well as in primary cultures of murine white, brite/beige and brown adipocytes, the N-acyl amino acids were proficient uncouplers but that they did not systematically display higher affinity or potency than the conventional fatty acids, and they were not as efficient uncouplers as classical protonophores (FCCP). Higher concentrations of the N-acyl amino acids (as well as of conventional fatty acids) were associated with signs of deleterious effects on the cells. In liver mitochondria, we found that the N-acyl amino acids uncoupled similarly to conventional fatty acids, thus apparently via activation of the adenine nucleotide transporter-2. In brown adipose tissue mitochondria, the N-acyl amino acids were able to activate UCP1, again similarly to conventional fatty acids. We thus conclude that the formation of the acyl-amino acid derivatives does not confer upon the corresponding fatty acids an enhanced ability to induce thermogenesis in peripheral tissues, and it is therefore unlikely that the N-acyl amino acids are of specific physiological relevance as UCP1-independent thermogenic compounds.

Combustion Synthesis of Nano Fe2O3 and its Utilization as a Catalyst for the Synthesis of Nα-Protected Acyl Thioureas and Study of Anti-bacterial Activities.

A simple and eco-friendly nano Fe2O3 heterogeneous catalytic system is described for the synthesis of acyl thiourea derivatives from corresponding in situ generated acyl isothiocyanates and amino acid esters in acetone obtained in good yields. The structures of synthesized acyl thioureas were confimed by 1H NMR, 13C NMR, mass, and FTIR analysis. Fe2O3 NPs has been prepared via a solution combustion route using ascorbic acid as the reducing agent and ferric nitrate as the source of iron. The prepared nano material has been characterized by XRD, SEM, UV-Visible, and FTIR analysis. More prominently, the Fe2O3 and other impurities are removed though a simple work-up and the material prepared shows to be effective in catalyzing the conversion of reactants to products in good yields. Further, some of the synthesized acyl thioureas were evaluated for in vitro antibacterial activity against Staphylococcus aureus and Escherichia coli.

Investigation of the enhanced oil recovery potential of sodium cocoyl alaninate: an eco-friendly surfactant

Amino acid-based surfactants (AASs) and other novel surfactants have recently gained attention to provide a favorable environmental image (“green”) in surfactant application. Yet their potential in enhancing oil recovery is not well investigated. Only a few works have been reported on their potential enhanced oil recovery (EOR) application with less satisfactory results. Here in, sodium cocoyl alaninate (SCA), an acylated amino acid with excellent properties that facilitate its application in other fields, is investigated for its EOR potential. Its effectiveness in lowering the interfacial tension and the emulsifying crude oil–brine mixture were studied. The ability to alter rock surface wettability and its adsorption behavior on the sand surface were studied as well. Then, its oil recovery potential was confirmed through a core displacement experiment. All studies were performed in comparison with conventionally deployed sodium dodecyl sulfate (SDS). The critical micelle concentrations for SCA (CMC = 0.23 wt%) and SDS (CMC = 0.21 wt%) were close, which serves as a good basis for comparing their EOR potential. SCA proved to be more effective in IFT reduction attaining a minimum IFT of 0.069 mN/m (i.e., ~ 98.8% IFT reduction) compared to 0.222 mN/m of SDS (i.e., ~ 96.2% IFT reduction) at the same concentration. Salinity showed a synergistic effect on the interfacial properties of both SCA and SDS but had a more significant impact on SDS interfacial properties than SCA due to low salt tolerance of SDS. The low IFT attained by SCA yielded enhanced emulsion formation and stable emulsion both at 25 °C and 80 °C for a period of one week. SCA also altered quartz surface wettability better via reduction of contact angle by 94.55% compared to SDS with contact angle reduction of 87.51%. The adsorption data were analyzed with the aid of various adsorption isotherm models. The adsorption behavior of SCA and SDS could be best described by the Langmuir model. This means a monomolecular surfactant layer exists at the aqueous–rock interface. SDS also exhibited more severe adsorption on the sand surface with the maximum adsorption density of 15.94 mg/g compared to SCA with the maximum adsorption density of 13.64 mg/g. The core flood data also confirmed that SCA has a better oil recovery potential than SDS with an additional oil recovery of 29.53% compared to 23.83% of SDS. This additional oil recovery was very satisfactory compared to the performance of other AAS that have been studied. This study therefore proves that SCA and other AAS could be outstanding alternatives to conventional EOR surfactants owing to their excellent EOR potential in addition to their environmental benign nature.

A Unique P450 Peroxygenase System Facilitated by a Dual-Functional Small Molecule: Concept, Application, and Perspective.

Cytochrome P450 monooxygenases (P450s) are promising versatile oxidative biocatalysts. However, the practical use of P450s in vitro is limited by their dependence on the co-enzyme NAD(P)H and the complex electron transport system. Using H2O2 simplifies the catalytic cycle of P450s; however, most P450s are inactive in the presence of H2O2. By mimicking the molecular structure and catalytic mechanism of natural peroxygenases and peroxidases, an artificial P450 peroxygenase system has been designed with the assistance of a dual-functional small molecule (DFSM). DFSMs, such as N-(ω-imidazolyl fatty acyl)-l-amino acids, use an acyl amino acid as an anchoring group to bind the enzyme, and the imidazolyl group at the other end functions as a general acid-base catalyst in the activation of H2O2. In combination with protein engineering, the DFSM-facilitated P450 peroxygenase system has been used in various oxidation reactions of non-native substrates, such as alkene epoxidation, thioanisole sulfoxidation, and alkanes and aromatic hydroxylation, which showed unique activities and selectivity. Moreover, the DFSM-facilitated P450 peroxygenase system can switch to the peroxidase mode by mechanism-guided protein engineering. In this short review, the design, mechanism, evolution, application, and perspective of these novel non-natural P450 peroxygenases for the oxidation of non-native substrates are discussed.

Identification, Characterization, and Synthesis of Natural Parasitic Cysteine Protease Inhibitors: Pentacitidins Are More Potent Falcitidin Analogues.

Protease inhibitors represent a promising therapeutic option for the treatment of parasitic diseases such as malaria and human African trypanosomiasis. Falcitidin was the first member of a new class of inhibitors of falcipain-2, a cysteine protease of the malaria parasite Plasmodium falciparum. Using a metabolomics dataset of 25 Chitinophaga strains for molecular networking enabled identification of over 30 natural analogues of falcitidin. Based on MS/MS spectra, they vary in their amino acid chain length, sequence, acyl residue, and C-terminal functionalization; therefore, they were grouped into the four falcitidin peptide families A-D. The isolation, characterization, and absolute structure elucidation of two falcitidin-related pentapeptide aldehyde analogues by extensive MS/MS spectrometry and NMR spectroscopy in combination with advanced Marfey's analysis was in agreement with the in silico analysis of the corresponding biosynthetic gene cluster. Total synthesis of chosen pentapeptide analogues followed by in vitro testing against a panel of proteases revealed selective parasitic cysteine protease inhibition and, additionally, low-micromolar inhibition of α-chymotrypsin. The pentapeptides investigated here showed superior inhibitory activity compared to falcitidin.

Neuroprotective potentials of selected natural edible oils using enzyme inhibitory, kinetic and simulation approaches

BackgroundEdible oils have proven health benefits in the prevention and treatment of various disorders since the establishment of human era. This study was aimed to appraise neuropharmacological studies on the commonly used edible oils including Cinnamomum verum (CV), Zingiber officinale (ZO) and Cuminum cyminum (CC).MethodsThe oils were analyzed via GC-MS for identifications of bioactive compounds. Anti-radicals capacity of the oils were evaluated via 2,2-diphenyl-1-picryl-hydrazyl-hydrate (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radicals scavenging assays. The samples were also tested against two important acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) which are among the important drug targets in Alzheimer’s disease. Lineweaver-Burk plots were constructed for enzyme inhibition studies which correspond to velocity of enzymes (Vmax) against the reciprocal of substrate concentration (Km) in the presence of test samples and control drugs following Michaelis-Menten kinetics. Docking studies on AChE target were also carried out using Molecular Operating Environment (MOE 2016.0802) software.Results(Gas chromatography-mass spectrometry GC-MS) analysis revealed the presence of thirty-four compounds in Cinnamon oil (Cv.Eo), fourteen in ginger oil (Zo.Eo) and fifty-six in cumin oil (Cc.Eo). In the antioxidant assays, Cv.Eo, Zo.Eo and Cc.Eo exhibited IC50 values of 85, 121, 280 μg/ml sequentially against DPPH radicals. Whereas, in ABTS assay, Cv.Eo, Zo.Eo and Cc.Eo showed considerable anti-radicals potentials with IC50 values of 93, 77 and 271 μg/ml respectively. Furthermore, Cv.Eo was highly active against AChE enzyme with IC50 of 21 μg/ml. Zo.Eo and Cc.Eo exhibited considerable inhibitory activities against AChE with IC50 values of 88 and 198 μg/ml respectively. In BChE assay, Cv.Eo, Zo.Eo and Cc.Eo exhibited IC50 values of 106, 101 and 37 μg/ml respectively. Our results revealed that these oils possess considerable antioxidant and cholinesterase inhibitory potentials. As functional foods these oils can be effective remedy for the prevention and management of neurological disorders including AD. Synergistic effect of all the identified compounds was determined via binding energy values computed through docking simulations. Binding orientations showed that all the compounds interact with amino acid residues present in the peripheral anionic site (PAS) and catalytic anionic site (CAS) amino acid residues, oxyanion hole and acyl pocket via π-π stacking interactions and hydrogen bond interactions.

Acyl Donor Stringency and Dehydroaminoacyl Intermediates in β-Lactam Formation by a Non-ribosomal Peptide Synthetase

Condensation (C) domains in non-ribosomal peptide synthetases catalyze peptide elongation steps whereby activated amino acid or peptidyl acyl donors are coupled with specific amino acid acceptors. In the biosynthesis of the β-lactam antibiotic nocardicin A, an unusual C domain converts a seryl tetrapeptide into its pentapeptide product containing an integrated β-lactam ring. While indirect evidence for the intermediacy of a dehydroalanyl species has been reported, here we describe observation of the elusive enzyme-bound dehydroamino acyl intermediate generated from the corresponding allo-threonyl tetrapeptide and partitioned into pentapeptide products containing either a dehydrobutyrine residue or an embedded β-lactam. Contrary to trends in the literature where condensation domains have been deemed flexible as to acyl donor structure, this β-lactam synthesizing domain is highly discriminating. The observation of dehydrobutyrine formation links this C domain to related clades associated with natural products containing dehydroamino acid and d-configured residues, suggesting a common mechanistic link.

Growth and metabolic responses of juvenile largemouth bass (Micropterus salmoides) to dietary vitamin c supplementation levels

To investigate the growth and metabolic responses of largemouth bass (Micropterus salmoides) to dietary vitamin c supplementation levels, quadruplicate groups of 30 largemouth bass juveniles were fed eight experimental diets with graded level of VC in cages floated in concrete tanks for 60 days. The result showed that growth, survival rate and digestive enzyme activity were strongly positively influenced by AMP100, AMP125 and AMP150. Treatment AMP125 significantly (P < 0.05) enhanced growth compared with AMP0, AMP25, AMP50 and AMP75. Tissue VC increased as VC level in diet increased, whole body crude protein and moisture were influenced by dietary VC supplementation. Dietary VC significantly influenced muscle amino acid and hepatic amino acyl transferase activity. Furthermore, AMP100, AMP125, AMP150 and AMP175 significantly triggered the up-regulation of Insulin-like growth factors (IGFs) and growth hormone (GH) gene mRNA expression level in liver and muscle compared with AMP0. Also, AMP125 and AMP150 maintained liver morphology. Nevertheless, dietary VC enhances digestive enzyme activity, hepatic amino acyl transferase activity and growth-related gene mRNA expression. Therefore, 120.46–145.35 mg/kg is adequate to improve the utilization of amino acid for growth, expression of growth-related genes and liver integrity in juvenile largemouth bass.

Experimental investigation of the behaviour of a novel amino acid-based surfactant relevant to EOR application

Acylated amino acids, a group of amino acid-based surfactants have been the focus of recent studies as green alternatives to petrochemical-based surfactants yet their enhanced oil recovery (EOR) potential is understudied. The few reported amino acid-based surfactants in literature showed less satisfactory performance compared to conventional surfactants with regards to their EOR application. In this present study, however, sodium cocoyl alaninate (SCA); an amino acid-based surfactant has been proven to have excellent properties relevant to its EOR application. It proved to have comparable or even better performance to commonly deployed surfactants for EOR application. Its surface activity and thermodynamic properties of aggregation are evaluated. The aggregation behaviour was considered employing surface tensiometry and conductometry data. With EOR application in mind, the interfacial tension (IFT) and wettability modification studies were made as well. The results were compared to conventional surfactants and other amino acid-based surfactants. SCA has surface tension reduction efficiency and effectiveness of 2.74 and 40.79 mN/m respectively compared to sodium dodecyl sulfate (SDS) with 2.51 and 32.5 mN/m. This proves that SCA is superior to SDS in terms of surface activity. Furthermore, with 91% reduction in IFT by SCA compared to 89% reduction by SDS, the superior surface activity of SCA to SDS was confirmed. There was evidence of synergy in reducing IFT when salt was added. About 47% improvement in IFT reduction was observed. SCA also has a superior ability to SDS and CTAB in modifying quartz and carbonate surfaces' wettability respectively. Quartz surface was altered from intermediate wet to water wet while carbonate surface was altered from oil wet to water wet. SCA, therefore, proves to be an excellent alternative to conventional EOR surfactants due to its superb surface activity coupled with its environmentally benign nature.

Identification of N-acyl amino acids that are positive allosteric modulators of glycine receptors

Glycine receptors (GlyRs) mediate inhibitory neurotransmission within the spinal cord and play a crucial role in nociceptive signalling. This makes them primary targets for the development of novel chronic pain therapies. Endogenous lipids have previously been shown to modulate glycine receptors and produce analgesia in pain models, however little is known about what chemical features mediate these effects. In this study, we characterised lipid modulation of GlyRs by screening a library of N-acyl amino acids across all receptor subtypes and determined chemical features crucial for their activity. Acyl-glycine’s with a C18 carbon tail were found to produce the greatest potentiation, and require a cis double bond within the central region of the carbon tail (ω6 – ω9) to be active. At 1 µM, C18 ω6,9 glycine potentiated glycine induced currents in α3 and α3β receptors by over 50%, and α1, α2, α1β and α2β receptors by over 100%. C18 ω9 glycine (N-oleoyl glycine) significantly enhance glycine induced peak currents and cause a dose-dependent shift in the glycine concentration response. In the presence of 3 µM C18 ω9 glycine, the EC5o of glycine at the α1 receptor was reduced from 17 µM to 10 µM. This study has identified several acyl-amino acids which are positive allosteric modulators of GlyRs and make promising lead compounds for the development of novel chronic pain therapies.

TECHNOLOGY OF SURFACE-ACTIVE RICINIC ACID DERIVATIVES

The overall purpose of the presented study is to determine the scientific basis of the technology amino acids based surfactants, this is relevant for Ukraine, because we dont have such production of domestic substances. The practical significance of the study is to use the surfactants obtained in the composition of detergents instead of alkyl sulfate salts. One of the varieties of environmentally friendly surfactants that have a gentle effect on human skin is acyl amino acids, which are obtained by the reaction of amino acids with fatty acids. A relatively simple to implement technology for biocompatible and biodegradable surfactants based on amino acids with the use of castor oil and aminoacetic acid as the main raw material is proposed. The results of IR spectroscopy show that the surfactants obtained are amides. Their basic surface-active properties are defined - surface tension and critical concentration of micelle formation. The obtained surfactants can be used in the composition of cosmetics and detergents, or independently in the form of an aqueous solution.

Dissipative Self-Assembly of Dynamic Multicompartmentalized Microsystems with Light-Responsive Behaviors

Summary Living cells are compartmentalized systems operating far from thermodynamic equilibrium and consume energy from the environment to carry out their functions. The construction of biomimetic synthetic compartments has both scientific and technological value. Despite many advances, the assembly of synthetic compartments that present nonequilibrium behaviors based on dissipative (or transient) self-assembly remains a grand challenge. Here, we describe the design and synthesis of multicompartmental systems with an active microstructure and complex behaviors. By including an artificial pathway for energy dissipation, we demonstrate the autonomous generation of active polymeric systems using a strategy based on polymerization-induced self-assembly (PISA), driven by chemical fuel. Remarkably, these self-organized synthetic systems exhibit a dynamic change in their multicompartmental structures when exposed to light. This work introduces a strategy toward the design and construction of synthetic compartments with a dynamic structure and also presents pathways to engineer materials with spatially controllable structures and functionalities.

N-acylation of L-amino acids in aqueous media: Evaluation of the catalytic performances of Streptomyces ambofaciens aminoacylases

N-acylated amino acids are widely used as surfactants and/or actives in cosmetics and household formulations. Their industrial production is based on the use of the Schotten-Baumann chemical and unselective reaction. Faced to the growing demand for greener production processes, selective enzymatic synthesis in more environment-friendly conditions starts to be considered as a potential alternative. This study concerns the use of the aminoacylases from Streptomyces ambofaciens to selectively catalyse aminoacid acylation reaction by fatty acids in aqueous medium. The results demonstrated that, when using undecylenoic acid as acyl donor, these aminoacylases properly catalyse the acylation of 14 of the 20 proteogenic l-amino acids tested on their α amino group with a great variability depending on the nature of the amino acid (polar or not, positively/negatively charged, aromatic or not…). More precisely, the following 9 amino acids were shown to be preferentially acylated by S. ambofaciens aminoacylases as follows: lysine > arginine > leucine > methionine > phenylalanine > valine > cysteine > isoleucine > threonine. Different fatty acids were used as acyl donors and, in most cases, the fatty acid length influenced the conversion yield. The kinetic study of α–lauroy-lysine synthesis showed a positive influence of lysine concentration with Vmax and Km of 3.7 mM/h and 76 mM, respectively. Besides, the lauric acid had an inhibitory effect on the reaction with Ki of 70 mM. The addition of cobalt to the reaction medium led to a more than six-fold increase of the reaction rate. These results, achieved with the aminoacylases from S. ambofaciens represent an improved enzyme-based N-acylated amino acids production in order to provide an alternative way to the Schotten-Baumann chemical reaction currently used in the industry.

Effect of Added Tetraalkylammonium Counterions on the Dilational Rheological Behaviors of N-Cocoyl Glycinate.

Ion specific effect, which is also known as Hofmeister effect, has been reported in numerous systems including ionic surfactant aggregates. Acyl amino acid surfactants have attracted growing attentions in the field of novel surfactants research due to their environmentally benign characteristics. The objective of this study was to investigate the effect of different salts containing NH4+ and tetraalkylammonium (TAA+), where alkyl = methyl (TMA+), ethyl (TEA+), and propyl (TPA+), cations on the dilational rheological properties of interfacial film are stabilized by potassium N-cocoyl glycinate (KCGl). The interfacial behaviors were studied using oscillating drop shape analysis method. The interfacial tensions (IFTs) and dilational rheological parameters results illustrate that KCGl in the presence of salts has better interfacial activity and stronger intermolecular interaction, indicating that added cations contribute to denser molecular packing at oil-water interface. Ion specific effects were observed in the system. Among the cations, KCGl shows highest dilational modulus in the presence of NH4+. The overall interaction between cations and headgroups of KCGl decreases in the sequence NH4+ >TMA+ >TEA+ ≈TPA+, which follows Hofmeister series. The increasing hydrophobicity of TAA+ prevents the interaction between cations and KCGl's headgroup, and therefore prevent amphiphiles from packing closely at interface. The results present a theoretical origin for useful application of KCGl in cosmetics, petroleum and daily chemical industries.

Green Synthesis, Characterization, and Properties of Acyl Lysine, Serine, Threonine, and Methionine Derived from Three Types of Natural Oils

AbstractThe development of environmentally benign products has been the subject of growing interest in the field of surfactant chemistry. Acyl amino acid surfactants bearing lysine, serine, threonine, and methionine residues were synthesized using natural oils extracted from coconut, palm kernel, and soybean as acyl donors. The chemical structures were confirmed by high‐performance liquid chromatography (HPLC/MS) and infrared (IR) spectra. Their surface activities, ion‐specific effects, detergency, and foam properties were studied systematically. The critical micelle concentration (CMC) values depend significantly on amino acid and oil types and follow the orders: (i) Lys &gt; Thr ≈ Ser &gt; Met and (ii) Coconut ≈ Palm kernel &gt; Soybean oil. Interestingly, the ion‐specific effects showing that the γCMC value decreases with increasing counterion size and hydrophobicity were observed, and the results were consistent with the famous Hofmeister series. The detergency ability of acyl amino acid surfactants is better than multiple traditional surfactants in distilled water. Although the detergency ability of our products for oil‐soiled swatches decreased significantly in hard water, this problem was solved by the C‐Lys‐Na/AES mixed system showing excellent synergistic effects. Excellent foamability and foam stability were achieved for acyl threonine and serine bearing hydroxyl groups on their headgroups, suggesting that the packing of these surfactants at the air–water interface was assisted by hydrogen bonding.

An excreted small molecule promotes C. elegans reproductive development and aging.

Excreted small-molecule signals can bias developmental trajectories and physiology in diverse animal species. However, the chemical identity of these signals remains largely obscure. Here we report identification of an unusual N-acylated glutamine derivative, nacq#1, that accelerates reproductive development and shortens lifespan in C. elegans. Produced predominantly by C. elegans males, nacq#1 hastens onset of sexual maturity in hermaphrodites by promoting exit from the larval dauer diapause and by accelerating late larval development. Even at picomolar concentrations, nacq#1 shortens hermaphrodite lifespan, suggesting a trade-off between reproductive investment and longevity. Acceleration of development by nacq#1 requires chemosensation and depends on three homologs of vertebrate steroid hormone receptors. Unlike ascaroside pheromones, which are restricted to nematodes, fatty acylated amino acid derivatives similar to nacq#1 have been reported from humans and invertebrates, suggesting that related compounds may serve signaling functions throughout Metazoa.

Synthesis of a burkholdine analogue containing β-hydroxytyrosine.

Synthesis of a β-OHTyr-containing Bk analogue, a cyclic octalipopeptide with antifungal activities, is described. Since β-OHTyr-containing peptides generally are unstable in strong acidic conditions, synthesis of β-HOTyr-containing peptides by SPPS have rarely been reported. To overcome this problem, we found that using distilled TFA removed the protecting groups of side chains of β-OHTyr-containing Bk analogue, which was prepared by Fmoc-SPPS. Abbreviations: β-OHTyr: β-hydroxytyrosine; β-OHAsn: β-hydroxyasparagine; Bk: burkholdine; FAA: fatty acyl amino acid; β-MeOTyr: β-methoxytyrosine; SPPS: solid phase peptide synthesis; MIC: minimun inhibitory concentration; DMF: dimethyl formamide; DIPEA: diisopropylethylamine; DIPC: diisopropylcarbodiimide; HOBt: 1-hydroxybenzotriazole; Fmoc: 9-fluorenylmethyloxycarbonyl; HFIP: 1,1,1,3,3,3-hexafluoropropan-2-ol; TFA: trifluoroacetic acid; LAP: N-lauryl -3-amino-4-carbamolypropanoic acid; HPLC: high performance liquid chromatography; ESI-TOFMS: electrospray ionization-time of flight mass spectrometry; Bn: benzyl; Boc: t-butyloxycatbonyl; 2-CTC: 2-chlorotritylchloride.

Genome-wide association study of feruloyl arabinoxylan content in common wheat grain

Arabinoxylan (AX) is an important component of dietary fiber, and exerts significant effects on the processing quality and nutritional value of flour. Feruloyl arabinoxylan (FAX) is a major factor influencing the functional properties of AX. Here, a genome-wide association study (GWAS) was conducted for FAX content using a high-density SNP platform. FAX content was evaluated in 256 wheat varieties (two populations) in four environments. Results showed that 83 and 33 marker-trait associations (MTAs) for FAX content were identified, explaining 6.7–9.2% and 10.2–21.2% phenotypic variation in the two populations. Two and three MTAs were repeatedly detected in at least two environments. Five MTAs were detected in both populations. Linear regression indicated a clear dependence of FAX content on the number of favorable alleles, indicating that QTL pyramiding would be an effective approach to modify FAX content. Associated with these significant MTAs, five candidate genes: isoflavone reductase, carnitine dehydrogenase, acylamino acid releasing enzyme, glucose isomerase, and GMP synthase were found to be involved in FAX biosynthesis. Lastly, our study contributes important information for genetic improvement of wheat quality and contributes to developing marker-assisted selection.

AntiSMASH 5.0: updates to the secondary metabolite genome mining pipeline.

Secondary metabolites produced by bacteria and fungi are an important source of antimicrobials and other bioactive compounds. In recent years, genome mining has seen broad applications in identifying and characterizing new compounds as well as in metabolic engineering. Since 2011, the ‘antibiotics and secondary metabolite analysis shell—antiSMASH’ (https://antismash.secondarymetabolites.org) has assisted researchers in this, both as a web server and a standalone tool. It has established itself as the most widely used tool for identifying and analysing biosynthetic gene clusters (BGCs) in bacterial and fungal genome sequences. Here, we present an entirely redesigned and extended version 5 of antiSMASH. antiSMASH 5 adds detection rules for clusters encoding the biosynthesis of acyl-amino acids, β-lactones, fungal RiPPs, RaS-RiPPs, polybrominated diphenyl ethers, C-nucleosides, PPY-like ketones and lipolanthines. For type II polyketide synthase-encoding gene clusters, antiSMASH 5 now offers more detailed predictions. The HTML output visualization has been redesigned to improve the navigation and visual representation of annotations. We have again improved the runtime of analysis steps, making it possible to deliver comprehensive annotations for bacterial genomes within a few minutes. A new output file in the standard JavaScript object notation (JSON) format is aimed at downstream tools that process antiSMASH results programmatically.