Sequential window acquisition of all theoretical mass spectra (SWATH-MS) as an emerging proteomics approach for the discovery of dark-cutting beef biomarkers.

Recent advances in "omics" technologies have enabled the identification of new beef quality biomarkers and have also allowed for the early detection of quality defects such as dark-cutting beef, also known as DFD (dark, firm, and dry) beef. However, most of the studies conducted were carried out on a small number of animals and mostly applied gel-based proteomics. The present study proposes for the first time a Sequential Window Acquisition of All Theoretical Mass Spectra (SWATH-MS) proteomics approach to characterize and comprehensively quantify the post-mortem muscle proteome of DFD (pH ≥ 6.

-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal-Metal Bond and the Photophysical Properties.

Precursors PtCl{κ--[py-CHMe-py]} (), PtCl{κ--[py-O-CH-O-py]} (), Pt(OH){κ--[py-CHMe-py]} (), and Pt(OH){κ--[py-O-CH-O-py]} () were used to prepare d-platinum bimetallic complexes. Precursors and react with AgBF and 7-azaindole (H) to give [Pt{κ--[py-CHMe-py]}{κ--[H]}]BF () and [Pt{κ--[py-O-CH-O-py]}{κ--[H]}]BF () and and with indolo[2,3-]indole (H) to generate Pt{κ--[H]}{κ--[py-CHMe-py]} () and Pt{κ--[H]}{κ--[py-O-CH-O-py]} (). Subsequent addition of and to - affords bimetallic derivatives [{Pt[κ--(py-CHMe-py)]}{μ--[]}]BF (), [{Pt[κ--(py-O-CH-O-py)]}{μ--[]}]BF (), and {Pt[κ--(py-CHMe-py)]}{μ--[]} ().

Exploring the miRNAs Profile in Dark-Cutting Beef.

In an animal production system, different stressors may cause the depletion of muscle glycogen stores, resulting in an elevated pH at 24 h (pH), which leads to cell metabolism alterations that affect the conversion of muscle into meat, causing meat quality defects, such as dark-cutting beef, also known as dark, firm, and dry (DFD) beef. This process may involve the alteration of small non-coding RNAs (miRNAs), which play critical regulatory roles in cellular processes. Here, we determined whether differential miRNA expression in the muscle from the Asturiana de los Valles breed at 24 h could serve as an early indicator of beef quality defects.

Muscle Hypertrophy Is Linked to Changes in the Oxidative and Proteolytic Systems during Early Tenderization of the Spanish Breed "Asturiana de los Valles".

For fresh meat consumers, eating satisfaction is of utmost importance and tenderness is one of the most important characteristics in this regard. Our study examined beef of different animal biotypes of the autochthonous breed "Asturiana de los Valles" (AV) to determine if early postmortem oxidative and proteolytic processes may influence the final tenderness of the product. This meat-specialized breed shows different biotypes depending on the frequency of a myostatin mutation "" that induces double-muscling or muscular hypertrophy (/, /+, +/+).

Two Synthetic Tools to Deepen the Understanding of the Influence of Stereochemistry on the Properties of Iridium(III) Heteroleptic Emitters.

Two complementary procedures are presented to prepare -pyridyl-iridium(III) emitters of the class [++] with two orthometalated ligands of the 2-phenylpyridine type () and a third ligand (). They allowed to obtain four emitters of this class and to compare their properties with those of the -pyridyl isomers. The finding starts from IrH(PPr), which reacts with 2-(-tolyl)pyridine to give -[Ir{κ--[CMeH-py]}] with an almost quantitative yield.

Preparation, Aromaticity, and Bromination of Spiro Iridafurans.

Iridium centers of [Ir(μ-Cl)(CH)] () activate the C(sp)-H bond of benzylideneacetone to give [Ir(μ-Cl){κ--[C(Ph)CHC(Me)O]}] (), which is the starting point for the preparation of the spiro iridafurans IrCl{κ--[C(Ph)CHC(Me)O]}(PPr) (), [Ir{κ--[C(Ph)CHC(Me)O]}(MeCN)]BF (), [Ir(μ-OH){κ--[C(Ph)CHC(Me)O]}] (), Ir{κ--[C(Ph)CHC(Me)O]}{κ--[CMeH-py]} (), and Ir{κ--[C(Ph)CHC(Me)O]}{κ--[acac]} (). The five-membered rings are orthogonally arranged with the oxygen atoms in in an octahedral environment of the iridium atom. Spiro iridafurans are aromatic.

Use of Near-Infrared Spectroscopy to Discriminate DFD Beef and Predict Meat Quality Traits in Autochthonous Breeds.

The potential of near-infrared reflectance spectroscopy (NIRS) to discriminate Normal and DFD (dark, firm, and dry) beef and predict quality traits in 129 Longissimus thoracis (LT) samples from three Spanish purebreeds, Asturiana de los Valles (AV; = 50), Rubia Gallega (RG; = 37), and Retinta (RE; = 42) was assessed. The results obtained by partial least squares-discriminant analysis (PLS-DA) indicated successful discrimination between Normal and DFD samples of meat from AV and RG (with sensitivity over 93% for both and specificity of 100 and 72%, respectively), while RE and total sample sets showed poorer results. Soft independent modelling of class analogies (SIMCA) showed 100% sensitivity for DFD meat in total, AV, RG, and RE sample sets and over 90% specificity for AV, RG, and RE, while it was very low for the total sample set (19.

Competition between ,,-Pincer and ,-Chelate Ligands in Platinum(II).

Replacement of the chloride ligand of PtCl{κ-,,-[py-CHR-py]} (R = H (), Me ()) and PtCl{κ-,,-[py-O-CH-O-py]} () by hydroxido gives Pt(OH){κ-,,-[py-CHR-py]} (R = H (), Me ()) and Pt(OH){κ-,,-[py-O-CH-O-py]} (). These compounds promote deprotonation of 3-(2-pyridyl)pyrazole, 3-(2-pyridyl)-5-methylpyrazole, 3-(2-pyridyl)-5-trifluoromethylpyrazole, and 2-(2-pyridyl)-3,5-bis(trifluoromethyl)pyrrole. The coordination of the anions generates square-planar derivatives, which in solution exist as a unique species or equilibria between isomers.

Role of the endoplasmic reticulum in the search for early biomarkers of meat quality.

Defects in meat quality such as dark, firm and dry (DFD) beef have been related to high levels of oxidative stress that produce cellular alterations that may affect to the process of meat quality acquisition. Despite the important role of endoplasmic reticulum (ER) in the cellular response to oxidative stress, its function in the muscle-to-meat conversion process has not yet been studied. In this study, differences in muscular antioxidant defense and the unfolded protein response (UPR) of the ER in CONTROL (normal pH) and dark, firm, and dry (DFD, pH ≥ 6.

Synthesis, Structure, and Photophysical Properties of Platinum(II) (,,') Pincer Complexes Derived from Purine Nucleobases†.

The synthesis of a series of Pt{κ-,,'-[L]}X (X = Cl, RC≡C) pincer complexes derived from purine and purine nucleosides is reported. In these complexes, the 6-phenylpurine skeleton provides the ,-cyclometalated fragment, whereas an amine, imine, or pyridine substituent of the phenyl ring supplies the additional '-coordination point to the pincer complex. The purine ,-fragment has two coordination positions with the metal (1 and 7), but the formation of the platinum complexes is totally regioselective.

Rhodium-Promoted C-H Bond Activation of Quinoline, Methylquinolines, and Related Mono-Substituted Quinolines.

The C-H bond activation of methylquinolines, quinoline, 3-methoxyquinoline, and 3-(trifluoromethyl)quinoline promoted by the square-planar rhodium(I) complex RhH{κ-P,O,P-[xant(PPr)]} [; xant(PPr) = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene] has been systematically studied. Results reveal that the activation of the heteroring is preferred over the activation of the carbocycle, and the activated position depends upon the position of the substituent in the substrate. Thus, 3-, 4-, and 5-methylquinoline reacts with to quantitatively form square-planar rhodium(I)-(2-quinolinyl) derivatives, whereas 2-, 6-, and 7-methylquinoline quantitatively leads to rhodium(I)-(4-quinolinyl) species.

New insights into the search of meat quality biomarkers assisted by Orbitrap Tribrid untargeted metabolite analysis and chemometrics.

Metabolite profiles of normal and defective dry, firm and dark (DFD) meat extracts with known ultimate pH (pHu) values were determined by Orbitrap Tribrid ID-X untargeted analysis coupled to chemometrics. An intelligent MS AcquireX workflow firstly approached the unambiguous characterization of detected features that were subsequently quantified by a complementary MS study of biological replicates. Chemometric research revealed how threonylphenylalanine (overexpressed in normal meats) together to tetradecadienoyl- and hydroxydodecanoyl-carnitines (both overexpressed in DFD meats) appropriately grouped meat groups assayed.

Development of a Portable Near-Infrared Spectroscopy Tool for Detecting Freshness of Commercial Packaged Pork.

Real-time monitoring of meat quality requires fast, accurate, low-cost, and non-destructive analytical methods that can be used throughout the entire production chain, including the packaged product. The aim of this work was to evaluate the potential of a portable near-infrared (NIR) spectroscopy tool for the on-site detection of freshness of pork loin fillets in modified atmosphere packaging (MAP) stored on display counters. Pork loin slices were sealed in MAP trays under two proportions of O2/CO2/N2: High-Ox-MAP (30/40/30) and Low-Ox-MAP (5/20/75).

C-Cl Oxidative Addition and C-C Reductive Elimination Reactions in the Context of the Rhodium-Promoted Direct Arylation.

A cycle of stoichiometric elemental reactions defining the direct arylation promoted by a redox-pair Rh(I)-Rh(III) is reported. Starting from the rhodium(I)-aryl complex RhPh{κ-P,O,P-[xant(PPr)]} (xant(PPr) = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene), the reactions include C-Cl oxidative addition of organic chlorides, halide abstraction from the resulting six-coordinate rhodium(III) derivatives, C-C reductive coupling between the initial aryl ligand and the added organic group, oxidative addition of a C-H bond of a new arene, and deprotonation of the generated hydride-rhodium(III)-aryl species to form a new rhodium(I)-aryl derivative. In this context, the kinetics of the oxidative additions of 2-chloropyridine, chlorobenzene, benzyl chloride, and dichloromethane to RhPh{κ-P,O,P-[xant(PPr)]} and the C-C reductive eliminations of biphenyl and benzylbenzene from [RhPh{κ-P,O,P-[xant(PPr)]}]BF and [RhPh(CHPh){κ-P,O,P-[xant(PPr)]}]BF, respectively, have been studied.

New Insights on the Impact of Cattle Handling on Post-Mortem Myofibrillar Muscle Proteome and Meat Tenderization.

This study investigated the effect of different cattle management strategies at farm (Intensive vs. Extensive) and during transport and lairage (mixing vs. non-mixing with unfamiliar animals) on the myofibrillar subproteome of et (LTL) muscle of "Asturiana de los Valles" yearling bulls.

Loss of microRNA-135b Enhances Bone Metastasis in Prostate Cancer and Predicts Aggressiveness in Human Prostate Samples.

About 70% of advanced-stage prostate cancer (PCa) patients will experience bone metastasis, which severely affects patients' quality of life and progresses to lethal PCa in most cases. Hence, understanding the molecular heterogeneity of PCa cell populations and the signaling pathways associated with bone tropism is crucial. For this purpose, we generated an animal model with high penetrance to metastasize to bone using an intracardiac percutaneous injection of PC3 cells to identify PCa metastasis-promoting factors.

Azolium Control of the Osmium-Promoted Aromatic C-H Bond Activation in 1,3-Disubstituted Substrates.

The hexahydride complex OsH(PPr) promotes the C-H bond activation of the 1,3-disubstituted phenyl group of the [BF] and [BPh] salts of the cations 1-(3-(isoquinolin-1-yl)phenyl)-3-methylimidazolium and 1-(3-(isoquinolin-1-yl)phenyl)-3-methylbenzimidazolium. The reactions selectively afford neutral and cationic trihydride-osmium(IV) derivatives bearing κ-- or κ--chelating ligands, a cationic dihydride-osmium(IV) complex stabilized by a κ--pincer group, and a bimetallic hexahydride formed by two trihydride-osmium(IV) fragments. The metal centers of the hexahydride are separated by a bridging ligand, composed of κ-- and κ--chelating moieties, which allows electronic communication between the metal centers.

A microRNA Cluster Controls Fat Cell Differentiation and Adipose Tissue Expansion By Regulating SNCG.

The H19X-encoded miR-424(322)/503 cluster regulates multiple cellular functions. Here, it is reported for the first time that it is also a critical linchpin of fat mass expansion. Deletion of this miRNA cluster in mice results in obesity, while increasing the pool of early adipocyte progenitors and hypertrophied adipocytes.

Assessment of Stress by Serum Biomarkers in Calves and Their Relationship to Ultimate pH as an Indicator of Meat Quality.

Seventy-eight calves from Asturiana de los Valles, Retinta, and Rubia Gallega breeds, under extensive and intensive farm systems and animal mixing and non-mixing conditions, and during the transport and lairage in slaughterhouses, were studied. This research aimed to study the effect of breed, farm system and mixing conditions on serum biomarkers (cortisol, lactate, glucose, serum amyloid A, haptoglobin, and C-reactive protein) and their relationship with pH at slaughter time, and to evaluate the response of the serum biomarkers of calves throughout fattening period. Moreover, this study aims to evaluate the response of the biomarkers in each breed during the fattening period.

Protein Biomarkers of Bovine Defective Meats at a Glance: Gel-Free Hybrid Quadrupole-Orbitrap Analysis for Rapid Screening.

An understanding of biological mechanisms that could be involved in the stress response of animal cattle prior to slaughter is critical to create effective strategies aiming at the production of high-quality meat. The sarcoplasmic proteome of directly extracted samples from normal and high ultimate pH (pHu) meat groups was studied through a straightforward gel-free strategy supported by liquid chromatography hybrid quadrupole-Orbitrap high-resolution mass spectrometry (LC-HRMS) analysis. A stepped proteomic pipeline combining rapid biomarker hunting supported by qualitative protein Mascot scores followed by targeted label-free peptide quantification revealed 26 descriptors that characterized meat groups assayed.

Impact of Extraction Method on the Detection of Quality Biomarkers in Normal vs. DFD Meat.

The objective of this work was to demonstrate how the extraction method affects the reliability of biomarker detection and how this detection depends on the biomarker location within the cell compartment. Different extraction methods were used to study the sarcoplasmic and myofibrillar fractions of the muscle of young bulls of the Asturiana de los Valles breed in two quality grades, standard (Control) or dark, firm, and dry (DFD) meat. Protein extractability and the expression of some of the main meat quality biomarkers-oxidative status (lipoperoxidation (LPO) and catalase activity (CAT)), proteome (SDS-PAGE electrophoretic pattern), and cell stress protein (Hsp70)-were analyzed.

Caspase activity in post mortem muscle and its relation to cattle handling practices.

Background: Animal handling practices are one of the factors majorly affecting animal metabolism prior to slaughter. This phenomenon increases the occurrence of meat quality defects such as dark cutting-beef, causing high economical losses in the meat industry. Under this framework, the assessment of apoptosis onset in post mortem muscle was proposed as a novel approach to reveal biochemical characteristics in several Spanish bovine breeds (Asturiana de los Valles, Retinta and Rubia Gallega) managed under different production systems (intensive versus semi-extensive) and transport/lairage conditions (mixing versus not mixing with unfamiliar animals).

Proteomic pipeline for biomarker hunting of defective bovine meat assisted by liquid chromatography-mass spectrometry analysis and chemometrics.

A wide variety of factors prior to slaughter may affect the stress status of beef cattle, giving rise to well-known 'dark-cutting' defective meats characterised by a high ultimate pH (pHu). To understand the underlying mechanisms of pHu fluctuations in beef cattle there was studied the proteome changes caused by pre-slaughter stress through a gel-free proteomic approach. Comparative peptidomic analysis was carried out on 12 loin samples at 24 h post-mortem from Longissimus thoracis et lumborum bovine muscle of crossbred animals, previously sorted into two different groups according to their pHu values: normal (pHu < 6.