Food-derived bioactive peptides as momentous food components: Can functional peptides passed through the PI3K/Akt/mTOR pathway and NF-κB pathway to repair and protect the skeletal muscle injury?

Muscle injury is defined as an overuse injury or traumatic distraction of a muscle, which is latent in any sport event, from amateur to large events. Based on previous numbers of muscle injuries and time spent to the athletes' recovery, the use of dietary functional factors intervention strategies is essential to enhance the recovery process and health. In recent years, there has been increasing evidence that biologically active peptides played an important role in sports nutrition and muscle injure recovery. Food-derived bioactive peptides were physiologically active peptides mostly derived from proteins following hydrolysis, which could be resorbed in intact form to reduce muscle damage following exercise and induce beneficial adaptions within the connective tissue. However, the complexity of the histoarchitectural considerations for skeletal muscle injuries and the repair mechanism of damaged skeletal muscle were not well known. In the following overview, the potential mechanisms and possible limitations regarding the damaged skeletal muscle metabolism were summarized, which aimed to present an overview of the nutritional strategies and recommendations after a muscular sports injury, emphasizing the use of main bioactive peptides. In addition, this review will provide implications for the studies of dietary bioactive peptides in the future.

Unraveling propylene glycol-induced lipolysis of the biosynthesis pathway in ultra-high temperature milk using high resolution mass spectrometry untargeted lipidomics and proteomics.

In July 2022, the food safety accident that excessive propylene glycol was detected in milk processing factory raised widespread concerns about quality and nutrition of milk with illegal additive. To the best of our knowledge, the influences of propylene glycol to lipids in milk had not been systematically explored. Therefore, spatiotemporal distributions of lipids related to propylene glycol reaction and changes of sensory quality were investigated by food exogenous. Briefly, 10 subclasses (Cer, DG, HexCer, LPC, LPE, PC, PE, PI, SPH and TG) included 147 lipids and 38 pivotal enzymes were annotated. Propylene glycol altered lysophospholipidase and phospholipase A2 through altering structural order in lipids domains surrounding proteins to inhibit glycerophospholipid metabolism and initiated obvious changes in PC (10.45-27.91 mg kg-1) and PE (12.92-49.02 mg kg-1). This study offered insights into influences of propylene glycol doses and storage time on milk metabolism at molecular level to assess the quality of milk.

Applications of lipidomics in goat meat products: Biomarkers, structure, nutrition interface and future perspectives.

Goat meat, as a superior product including low lipids, low cholesterol contents and high-quality proteins, becomes the superior food for the national market. With the increasing demand for goat meat, the production, sensory quality and physicochemical properties of goat meat are also widely observed. Following significant discoveries on the mechanism determining goat meat quality, further research on complex and interactive factors leading to changes of goat meat quality is increasingly based on data-driven "omics" methods, such as lipidomics, which can rapidly identify and quantify >1000 lipid species at same time facilitating comprehensive analyses of lipids in tissues. Molecular mechanism and biomarkers indicating the changes of goat meat quality, authentication, meat analogue, nutrition and health by lipidomics are feasible. According to the analysis results of the classes and of different biomarkers lipids of goat meat quality, the main processes involved the biosynthesis of unsaturated fatty acids, associations with lipids and proteins, lipid oxidation, lipid hydrolysis, lipid degradation, lipid deposition and lipid denaturation, which have been translated into advanced technologies for identifying the goat meat adulteration and faux meat rapidly and accurately. SIGNIFICANCE: In this review, the research of lipidomics technology, past applications, recent findings and common on the recent advances of lipidomics in the quality assessment of mutton products by lipidomics with MS approaches have been summarized. The information reported in review can serve as a reference to characterize the lipids found in mutton, clarify the application of lipidomics to the field of mutton products and provide new perspectives in producing superior quality mutton products.

Amphiphilic Low-Molecular-Weight Gelators Bearing ß-S-N-Acetylglucosamine Linked to a Tartaric Acid Scaffold: Synthesis, Self-Assembly and Wheat Germ Agglutinin Binding.

The self-assembly of carbohydrate-based amphiphiles can lead to colloidal soft materials such as supramolecular gels featuring highly desirable characteristics like biodegradability and biocompatibility. The report herein presents the synthesis, characterization and supramolecular self-assembly, physical gelation and wheat lectin binding of two structurally related amphiphilic compounds having ß-S-N-acetylglucosamine residues linked to a 2,3-diacyl-N,N'-dipropargylated-l-tartaric diamide. A 1-thio-ß-N-acetyl-d-glucosamine precursor attached to a conveniently functionalized linker with an azido group was synthesized by means of a one-pot procedure followed by deprotection. A click reaction successfully led to the two amphiphiles, which differed in length of the fatty acid attached to the tartaric acid scaffold. Although both compounds are poorly soluble in water and organic solvents, the difference in terms of hydrophilic moieties provided them with distinct supramolecular gelation properties. While the presence of an octadecyl chain produced a hydrogelator, the dodecadecyl homologue would only form weak gels in DMSO. SEM and rheology experiments confirmed the characteristic fibrillar morphology and viscoelastic properties, in agreement with the presence of physical gels. Both amphiphiles were able to interact reversibly with wheat germ agglutinin (WGA), a lectin that specifically recognizes GlcNAc residues, indicating a potential use in the food industry, as a gluten sensitivity manager, as well as in health-related industries, for example, for drug delivery systems.

Rhodium(II)-Catalyzed Enantioselective Intermolecular Aziridination of Alkenes.

C4-Symmetrical dirhodium(II) tetracarboxylates are highly efficient catalysts for the asymmetric intermolecular aziridination of substituted alkenes with sulfamates. The reaction proceeds with high levels of efficiency and chemoselectivity to afford aziridines with excellent yields of up to 95% and enantiomeric excesses of up to 99%. The scope of the alkene aziridination includes mono-, di-, and trisubstituted olefins as well as the late-stage functionalization of complex substrates. The reaction can be performed on a gram-scale with a catalyst loading of 0.1 mol %. Our DFT study led us to propose a two-spin-state mechanism, involving a triplet Rh-nitrene species as key intermediate to drive the stereocontrolled approach and activation of the substrate.

Hydrogen bonds and hydrophobicity with mucin and α-amylase induced honey aroma in Feng-flavor Baijiu during 16 years aging.

Honey aroma is one of the most significant factors of Feng-flavor Baijiu, which is also an essential element to attract consumers. However, the evaluation and chemical basis of honey aroma is unclear. Palmitoleic acid, lagochilin, phomotenone and ethyl behenate were confirmed to be the strongest contributors to honey aroma by time-intensity analysis and UHPLC-Q-Orbitrap-MS. Predictive modeling was developed for processing honey aroma intensity responses in order to obtain significant Feng-flavor Baijiu rankings. In this study, the effects of ex-vivo saliva on Feng-flavor Baijiu were investigated for the first time. Mucin and α-amylase, as major proteins in ex-vivo saliva, were applied to simulate molecular docking of ethyl benzoate. Mucin and α-amylase modified the aroma release, which depended on hydrogen bonds and hydrophobic interactions, respectively. It is blazing a trail in the field in sensory experience of Feng-flavor Baijiu as well as contributes to our understanding of Feng-flavor Baijiu drinking process.

Ethyl carbamate regulate esters degradation by activating hydrolysis during Baijiu ripening.

The presence of ethyl carbamate in traditional fermented food is a public health concern for the FDA. The effect of forced photoirradiation (0-150,000 lx) and thermal stress (4, 25, 40 °C) on ethyl carbamate (0-150 µg/L) on physiological characteristics of Baijiu, such as esters content, photochemical degradation, and hydrogen-bond interaction efficiency were monitored by ultra high performance liquid chromatography quadrupole-orbitrap and the dynamic changes by digital foodomics analysis. Furthermore, 748 trace components covering 11 subclasses were identified in Baijiu and 71 esters were screened by Spearman's correlation, fold changes, P values and VIP values. A forward stepwise multiple regression and discriminant analysis were performed for predicting the content of esters from appearance characteristics obtained by foodomics analysis, reaching R-square values up to 0.91. A reduction of the present variation in ethyl lactate, ethyl caproate, diethyl succinate, ethyl oleate and ethyl linoleate concentration could possibly result in a better understanding of the ethyl carbamate effects. Ethyl carbamate was found to cause esters hydrolysis through inter-molecular interaction in various species of alcoholic drinks. It was demonstrated that the light exposure level and thermal intensity applied for ethyl carbamate-spiked Baijiu samples did not unambiguously influence esters concentration in Baijiu. Future research should focus on moderate light exposure level and thermal stress and should aim at reducing natural ethyl carbamate by more closely controlling the esters content of the ripening degree.

Application of liquid chromatography mass spectrometry-based lipidomics to dairy products research: An emerging modulator of gut microbiota and human metabolic disease risk.

Lipids in dairy products, as the crucial components in the most essential biological processes, were among the many nutrients delivered to the infants and adults. The structures of lipids are not only intricate but also varied, which makes the holistic and systematic analyses challenging. In recent years, lipidomics, as the new promoter of lipomics in the omics era, has become one of the fastest growing scientific disciplines in food science research. In addition, lipidomics is also one of the major methods to explore the dynamic changes and chemical compositions of lipids in dairy products in recent years. It is a relatively new frontier of intermolecular interactions research, using advanced liquid chromatography mass spectrometry technology to explore lipids. In this paper, the latest progress of liquid chromatography mass spectrometry based lipidomics was reviewed, with emphasis on the application of lipidomics and metabolic disease risk in dairy research. This includes a detailed workflow for routine lipidomics analysis, as well as examples of applications devoted dairy foods components, quality, safety, and revealing the health benefits of dairy products lipids. Advanced and effective methods of MS promote the in-depth study of gut microbiota and human metabolic disease risk and provide tangible solutions for further research in this field.

Editorial on Special Issue "Organogels: State of the Art".

Organogels are a very diverse and fascinating class of soft materials that, over the last 30 years, have evolved to be one of the most interesting subjects in materials science [...].

Synthesis, self-assembly and Langerin recognition studies of a resorcinarene-based glycocluster exposing a hyaluronic acid thiodisaccharide mimetic.

Herein, we report the synthesis of an octavalent glycocluster exposing a thiodisaccharide mimetic of the repetitive unit of hyaluronic acid, ßSGlcA(1 → 3)ßSGlcNAc, constructed on a calix[4]resorcinarene scaffold by CuAAC reaction of suitable precursors. This glycocluster showed a strong tendency toward self-aggregation. DOSY-NMR and DLS experiments demonstrated the formation of spherical micelles of d ≅ 6.2 nm, in good agreement. TEM micrographs showed the presence of particles of different sizes, depending on the pH of the starting solution, thus evidencing that the negative charge on the micelle surface due to ionization of the GlcA residues plays an important role in the aggregation process. STD-NMR and DLS experiments provided evidence of the interaction between the synthetic glycocluster and Langerin, a relevant C-type lectin. This interaction was not observed in the STD-NMR experiments performed with the basic disaccharide, providing evidence of a multivalent effect.

Multivalent assembly of a pyrene functionalized thio-N-acetylglucosamine: Synthesis, spectroscopic and WGA binding studies.

We introduce here a new fluorescent derivative of 1-thio-ß-N-acetylglucosamine linked to a pyrene system through a triazolylpentyl spacer, designed to self-assemble into a multivalent glycocluster. The synthesis was achieved by efficient CuAAC click reaction between a pyrene functionalized with an azide group and a suitable alkynyl thiomonosaccharide. Spectroscopic studies by fluorometry indicated that the self-assembly in aqueous medium is modulated by concentration and pH changes, the latter due to the presence of the amino group close to the π system. Circular dichroism experiments revealed a moderate positive signal, suggesting that the pyrene-thioGlcNAc conjugate can aggregate into a chiral supramolecular assembly. The sugar moiety showed to specifically and reversibly interact with the wheat germ agglutinin, a fact that was demonstrated by turbidity assay. SEM microscopy of a lyophilized solution at pH 10 revealed a fibrillar morphology compatible with the presence of tubular micelles, whereas crystalline and amorphous solids are formed at lower pHs.

Late-stage C-H amination of abietane diterpenoids.

This study aims at highlighting the synthetic versatility of the rhodium-catalyzed C-H amination reactions using iodine(iii) oxidants for the late-stage functionalization of natural products. Inter- and intramolecular nitrene insertions have been performed from various abietane diterpenoids, leading to the amination of the C-3, C-6, C-7, C-11 and C-15 positions. Ca. 20 aminated compounds have been isolated with yields of up to 86% and high levels of regio-, chemo- and stereoselectivities.

Gels as Templates for the Syntheses of Shape-Controlled Nanostructured Materials.

The preparation of inorganic, organic and/or hybrid nanostructured materials with controlled shape and size is crucial for the development of nanotechnology, and it is nowadays the focus of intense research.[...].

Synthesis of new C-25 and C-26 steroidal acids as potential ligands of the nuclear receptors DAF-12, LXR and GR.

A new methodology to obtain C-25 and C-26 steroidal acids starting from pregnenolone is described. Construction of the side chain was achieved by applying the Mukaiyama aldol reaction with a non-hydrolytic work-up to isolate the trapped silyl enol ether with higher yields. Using this methodology we synthesized three new steroidal acids as potential ligands of DAF-12, Liver X and Glucocorticoid nuclear receptors and studied their activity in reporter gene assays. Our results show that replacement of the 21-CH3 by a 20-keto group in the side chains of the cholestane scaffold of DAF-12 or Liver X receptors ligands causes the loss of the activity.

Supramolecular Assembly of pH-Sensitive Triphenylene Derived π-Gelators and Their Application as Molecular Template for the Preparation of Silica Nanotubes.

The gelation properties and mode of self-assembly of six asymmetrical hexaether triphenylene derivatives mono-functionalized with carboxylic and primary amine groups were investigated. The presence of a carboxylic and amine group attached to the triphenylene core generated stable, thermo- and pH-sensitive supramolecular π-organogels with a reversible response to both stimuli. In order to understand the gelation process, we studied the effect of the spacer length and found a different gelation scope for the acid and basic derivatives that accounts for a different supramolecular self-assembly. The presence of the basic group on the amino derivatives was used to guide and catalyze the templated in situ sol-gel polymerization of TEOS and allowed us, under controlled hydrolytic conditions, to prepare an entangled fibrillar network of silica nanotubes.

Versatile supramolecular organogel with outstanding stability toward aqueous interfaces.

In this communication, we report on a novel and versatile low-molecular-weight organogelator. The methanolic gel exhibits an exceptional water-enhanced stability as evidenced by a 30 °C increase in Tg with up to 10%v/v of water. This atypical property not observed with other solvents makes of this supramolecular gel a highly stable matrix compatible with aqueous interfaces. As a proof of principle we present the sensing performance of a symmetric tricarbocyanine fluorophore bearing a Zn(II)chelator unit. The system retained its remarkable physical integrity for a long period of time opening new possibilities for other organic-aqueous interface applications.

Self-assembly of 2,3-dihydroxycholestane steroids into supramolecular organogels as a soft template for the in-situ generation of silicate nanomaterials.

Supramolecular gels are an important and interesting class of soft materials that show great potential for many applications. Most of them have been discovered serendipitously, and understanding the supramolecular self-assembly that leads to the formation of the gel superstructure is the key to the directed design of new organogels. We report herein the organogelating property of four stereoisomers of the simple steroid 2,3-dihydroxycholestane. Only the isomer with the trans-diaxial hydroxy groups had the ability to gelate a broad variety of liquids and, thus, to be a super-organogelator for hydrocarbons. The scope of solvent gelation was analysed with regard to two solvent parameters, namely the Kamlet-Taft and the Hansen solubility parameters. The best correlation was observed with the Hansen approach that revealed the existence of two clear gelation zones. We propose a general model of self-assembly through multiple intermolecular hydrogen bonds between the 1,2-dihydroxy system, which is based on experimental data and computational simulations revealing the importance of the di-axial orientation of the hydroxy groups for the one-dimensional self-assembly. Under controlled conditions, the fibrillar superstructure of the organogel was successfully used as a template for the in-situ sol-gel polymerization of tetraethoxysilane and the further preparation of silica nanotubes. We propose that the driving forces for templating are hydrogen bonding and electrostatic interactions between the anionic silicate intermediate species and the self-assembled fibrillar network.

Synthesis of 6-azaprogesterone and 19-hydroxy-6-azasteroids.

19-Hydroxy-6-azapregnanes were obtained from pregnenolone via a 7-azido-5-oxo-6-nor-5,7-secopregnane intermediate. The 6-azapregnane core was built in good yield in a straightforward way from the secosteroid, by means of a Staudinger (aza-Wittig) reaction. Finally the 19-hydroxy-6-azapregnane was transformed into 19-hydroxy-6-azaprogesterone (that cyclized spontaneously to the 19→3 hemiketal) and 6-azaprogesterone. The 6-azapregnanes lacked agonistic/antagonistic activity on the progesterone receptor.

Biological activity and ligand binding mode to the progesterone receptor of A-homo analogues of progesterone.

The biological activity of two seven-membered A-ring (A-homo) analogues of progesterone was evaluated by transactivation assays in Cos-1 cells and by determination of Bcl-x(L) expression levels in T47D cells. The results show that both compounds act as selective progesterone receptor (PR) agonists but lack mineralocorticoid receptor (MR) activity. Molecular modelling using semiempirical AM1 and ab initio HF/6-31G** calculations, showed that the A-ring of the A-homo steroids may adopt five different conformations, although only three correspond to low energy conformers. The low energy conformers of each analogue were introduced into the ligand binding pocket of the PR ligand binding domain (LBD) obtained from the PR LBD-progesterone crystal structure. The steroid binding mode was then analyzed using 10 ns of molecular dynamics (MD) simulation. The PR LBD-progesterone complex was also simulated as a control system. The MD results showed that both A-homo steroids have one conformer that may be properly recognized by the PR, in agreement with the observed progestagen activity. Moreover, the simulation revealed the importance of a water molecule in the formation of a hydrogen bonding network among specific receptor residues and the steroid A-ring carbonyl.

Synthesis and GABAA receptor activity of A-homo analogues of neuroactive steroids.

A procedure is described for the preparation of A-homo-5-pregnenes via an acid catalyzed rearrangement of cyclopropylcarbinols assisted by microwave irradiation. 3alpha-Hydroxy and 4alpha-hydroxy-A-homo-5-pregnen-20-one, analogues of the neuroactive steroid allopregnanolone, were obtained by means of a regioselective epoxidation of a double bond in the expanded A-ring, using a fructose-derived chiral ketone as catalyst and oxone as oxidant. Although both these compounds were marginally active in inhibiting TBPS binding to GABA(A) receptors, 3beta-hydroxy-A-homo-5-pregnen-20-one was almost as active as allopregnanolone. Reduction of the double bond of the latter compound resulted in a ten fold loss of activity.