Histidine (His) carries a unique heteroaromatic imidazole side chain and plays irreplaceable functional roles in peptides proteins. Existing strategies for site-selective histidine modification predominantly rely on the N-substitution reactions of moderately nucleophilic group, which inherently suffers from interferences lysine cysteine residues. Chemoselective remains one most difficult challenges peptide chemistry. Herein, we report via radical-mediated chemoselective C–H alkylation using...

Nanoscale small extracellular vesicles (sEVs, exosomes) in tears allow us to investigate the multisignatures of diseases. However, translations tear sEVs for biomarker discovery and clinical diagnostics are practically limited by low recovery, long processing time, sample volume. Here, we report an incorporated tear-exosomes analysis via rapid-isolation system (iTEARS) nanotechnology discover secrets ocular disorders systemic We isolate exosomes rapidly with high yield purity from a few...

Glycogen metabolism commonly altered in cancer is just beginning to be understood. Phosphoglucomutase 1 (PGM1), the first enzyme glycogenesis that catalyzes reversible conversion between glucose 1-phosphate (G-1-P) and 6-phosphate (G-6-P), participates both breakdown synthesis of glycogen. Here, we show PGM1 down-regulated hepatocellular carcinoma (HCC), which associated with malignancy poor prognosis HCC. Decreased expression obstructed pathway, leads increased flow into glycolysis, thereby...

Low-temperature storage is the primary postharvest method employed to maintain fruit quality and commercial value. However, pitting can develop during refrigeration, especially shelf life. In this study, a membrane lipidomic approach was analyze potential relationship between lipid metabolism post-cold-storage We also determined changes in ultrastructure water distribution by low-field nuclear magnetic resonance (LF-NMR) assessed permeability of membrane, peroxidation, proline...

Sulfur and selenium occupy a distinguished position in biology owing to their redox activities, high nucleophilicity, acyl transfer capabilities. Thiolated/selenolated amino acids, including cysteine, selenocysteine, derivatives, play critical roles regulating the conformation function of proteins serve as an important motif for peptide design bioconjugation. Unfortunately, general concise method attain enantiopure β-thiolated/selenolated acids remains unsolved problem. Herein, we present...

Native chemical ligation (NCL) provides a powerful solution to assemble proteins with precise features, which enables detailed investigation of the protein structure–function relationship. As an extension NCL, discovery desulfurization and expressed (EPL) techniques has greatly expanded efficient access large or challenging sequences via ligations. Despite its superior reliability, NCL-desulfurization protocol requires orthogonal protection strategies allow selective in presence native Cys,...

Harnessing the potential of tumor-associated macrophages (TAMs) to engulf tumor cells offers promising avenues for cancer therapy. Targeting phagocytosis checkpoints, particularly CD47-signal regulatory protein α (SIRPα) axis, is crucial modulating TAM activity. However, single checkpoint inhibition has shown a limited efficacy. In this study, we demonstrate that ferrimagnetic vortex-domain iron oxide (FVIO) nanoring-mediated magnetic hyperthermia effectively suppresses expression CD47 on...

Naturally abundant quinones are important molecules, which play essential roles in various biological processes due to their reduction potential. In contrast universality, the investigation of reactions between and proteins remains sparse. Herein, we report development a convenient strategy protein modification via biomimetic quinone-mediated oxidation at N-terminus. By exploiting unique reactivity an ortho-quinone reagent, α-amine N-terminus is oxidized generate aldo or keto handle for...

Summary Chilling stress has seriously limited the global production and geographical distribution of rice. However, molecular mechanisms associated with plant responses to chilling are less known. In this study, we revealed a member β‐ketoacyl‐ACP synthase I family (KASI), OsKASI‐2 which confers tolerance in encodes chloroplast‐localized KASI enzyme mainly expressed leaves anthers rice strongly induced by stress. Disruption led decreased KAS enzymatic activity levels unsaturated fatty acids,...

Indoleamine 2,3-dioxygenase (IDO), highly expressed in hepatocellular carcinoma (HCC), plays a pivotal role creating an immune-suppressive tumor microenvironment. Inhibiting IDO activity has emerged as promising immunotherapeutic strategy; however, the delivery of inhibitors to site is constrained, limiting their therapeutic efficacy. In this study, we developed magnetic vortex nanodelivery system for targeted inhibitor NLG919, integrated with hyperthermia therapy reverse microenvironment...

The use of native chemical ligation at selenocysteine (Sec) residues with peptide thioesters and additive-free selenocystine peptides bearing phenyl selenoesters, in concert one-pot oxidative deselenization chemistry, is described. These approaches provide a simple rapid method for accessing serine place Sec the junction. efficiency both variants ligation-oxidative chemistry probed through synthesis MUC5AC-derived glycopeptide.

Blueberry (Vaccinium spp.) is a small berry with high economic value. Although cold storage can extend the time of blueberry to more than 60 days, it leads chilling injury (CI) displaying as pedicle pits; and samples 0 °C-30 days was critical point CI. However, little known about mechanism molecular basis response stress in have not been explained definitely. To comprehensively reveal CI mechanisms stress, we performed high-throughput RNA Seq analysis investigate gene regulation network 0d...

Sini Decoction (SND), as a classic prescription of Traditional Chinese Medicine (TCM), has been proved to be clinically useful in cardiomyopathy and inflammatory bowel diseases. However, the role mechanism SND colitis-associated cancer remains unclear. This study aims evaluate effect on colorectal cancer(CRC) symptoms further explore changes gut microbes mediated by extract azoxymethane (AOM)/dextran sulfate sodium (DSS)-induced CRC mice through 16 S rRNA sequencing. Our results indicated...

Site-selective peptide functionalization provides a straightforward and cost-effective access to diversify peptides for biological studies. Among many existing non-invasive conjugations methodologies, photoredox catalysis has emerged as one of the powerful approaches site-specific manipulation on native peptides. Herein, we report highly N-termini-specific method rapidly itaconated their derivatives through combination transamination conditions. This strategy exploits facile reactivity...

Extracellular vesicle (EV) cargos with regular fluctuations hold the potential for providing chemical predictors toward clinical diagnosis and prognosis. A plasma sample is one of most important sources circulating EVs, yet technical barrier cost consumption in plasma-EV isolation still limit its application disease biomarker discovery. Here, we introduced an easy-to-use strategy that allows selectively purifying small EVs (sEVs) from human detecting their metabolic alternations. Fe3O4@TiO2...

Magnetothermodynamic (MTD) therapy can activate antitumor immune responses by inducing potent immunogenic tumor cell death. However, development is often accompanied multifarious immunosuppressive mechanisms that counter the efficacy of MTD therapy. High-mobility group protein A1 (HMGA1) overexpressed within hepatocellular carcinoma tissues and plays a crucial function in generation effects. The reversal HMGA1-mediated immunosuppression could enhance death-induced responses. A ferrimagnetic...

Reprogramming anti-inflammatory macrophages into pro-inflammatory type becomes an efficient antitumor therapeutic approach. With the development of nanotechnology, strategy using nanomaterials is effective option for TAM repolarization.

We describe the synthesis and incorporation of α- β-configured rhamnosyl arginine cassettes into <italic>Pseudomonas aeruginosa</italic> elongation factor P-derived glycopeptides. These were used to unequivocally determine native anomeric configuration rhamnose moiety in EF-P.