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Milk‐derived exosomes (MDEs), being a component of milk, have the potential to support immune system maturation in offspring and enhance immune cell proliferation. Through the transport and transmission of essential signaling molecules, MDEs contribute to the regulation of intergenerational and intraspecies communication, thereby impacting nutrient uptake and metabolic functions. A comprehensive comprehension of MDE functionalities is imperative for enhancing the quality of the dairy industry. A systematic search of the databases PubMed/Medline, Web of Science, and Scopus utilizing predetermined keywords resulted in the identification of 418 articles, of which 67 were chosen for inclusion in this review, which specifically explores the intersection of immune response and nutrition. This article provides a critical analysis of the classification of extracellular vesicles, the mechanisms underlying the biosynthesis of microvesicular dietary exosomes (MDEs), the components of MDEs, and their relevance in the contexts of nutrition and immune modulation. The primary aim of this review was to offer valuable scholarly insights to support the advancement and practical application of MDEs. [ABSTRACT FROM AUTHOR]

• The diatom assemblages are closely correlated with the environmental variables. • Three assemblages are distinguished with different hydrological characteristics. • Important for palaeoceanographic studies in the northern and middle Okinawa Trough. Determining the relationship between diatoms in surface sediments and the local sedimentary environment is important for paleoenvironmental reconstruction, including in marine settings. In this study, we used canonical correspondence analysis of 41 surface sediment samples from the northern and middle Okinawa Trough to analyze the relationship between diatom species and environmental variables. The principal results are as follows. (i) The diatom assemblages are closely correlated with the environmental variables, specifically, July sea surface salinity (SSS-Jul), February sea surface temperature (SST-Feb), and June sea surface temperature (SST-Jun). (ii) Three diatom assemblages are distinguished, representing environments with different hydrological characteristics. The high-temperature diatom assemblage may indicate a warm-water mass (the Kuroshio Current), and the polyhaline diatom assemblage can be used as an indicator of a high salinity water mass. The mixed diatom assemblage is associated with the warm-water masses of the Kuroshio Current, and shelf water masses with a low salinity and low temperature. (iii) The high-temperature and mixed diatom assemblages occur on the boundary of the continental shelf and Okinawa Trough, and are temperature sensitive; the high-temperature assemblage is located further upstream of the Kuroshio Current, indicating higher temperatures. Changes in the distribution of the polyhaline diatom assemblage within sediment cores can be regarded as an indicator of changes in water masses, and of possible salinity variations, in this area. These three assemblages are potentially important for future palaeoceanographic studies. [ABSTRACT FROM AUTHOR]

In this study, a series of H‐bonded arylamide foldamers bearing benzoselenadiazole ends with solvent‐responsive properties have been synthesized. In dichloromethane or dimethyl sulfoxide solvents, the molecules exhibit meniscus or linear structures, respectively, which can be attributed to the unique intramolecular hydrogen bonding behavior evidenced by 1D 1H NMR and 2D NOESY spectra. UV‐vis spectroscopy experiments show that the absorption wavelength of H‐bonded arylamide foldamers are significantly red‐shifted due to the presence of benzoselenadiazole group. In addition, the crystal structures reveal that effective intermolecular dual Se ⋅ ⋅ ⋅ N interactions between benzoselenadiazole groups induce further assembly of the monomers. Remarkably, supramolecular linear and double helices structures are constructed under the synergistic induction of intramolecular hydrogen bonding and intermolecular chalcogen bonding. Additionally, 2D DOSY diffusion spectra and theoretical modelling based on density functional theory (DFT) are performed to explore the persistence of intermolecular Se ⋅ ⋅ ⋅ N interactions beyond the crystalline state. [ABSTRACT FROM AUTHOR]

In this study, a benzoselenadiazole- and pyridine-bifunctionalized hydrogen-bonded arylamide foldamer was synthesized. A co-crystallization experiment with 1,4-diiodotetrafluorobenzene showed that a new type of supramolecular double helices, which were induced by three orthogonal interactions, namely, three-center hydrogen bonding (O⋯H⋯O), I⋯N halogen bonding and Se⋯N chalcogen bonding, have been constructed in the solid state. This work presents a novel instance of multiple non-covalent interactions that work together to construct supramolecular architectures. [ABSTRACT FROM AUTHOR]

[Display omitted] • Complexes 1a , 1b , 2a , 2b , 3a and 3b contain a stable four-membered chelating ring. • The modulation of the luminescence color from green to blue-green and red was achieved. • The OLEDs based on 1a , 1b , 2a , 2b , 3a and 3b exhibit low efficiency roll-off. Six dpppy (P,P-diphenyl-N-(pyridin-2-yl)phosphinic amide)- and dppq (P,P-diphenyl-N-(quinolin-2-yl)phosphinic amide)-based iridium(III) complexes 1a , 1b , 2a , 2b , 3a and 3b containing four-membered chelate architecture were synthetized. Their crystal structure and photophysical properties were investigated. The crystal structure shows that two coordinating N atoms from the ancillary ligand dpppy and dppq form a four-membered chelate architecture with the centered iridium(III). By changing the substituent groups and conjugation of the cyclometalated ligand, the control of the luminescent color of the complexes was achieved. In CH 2 Cl 2 solution, complexes 1a , 1b , 2a , 2b , 3a and 3b emitted phosphorescence peaked at 509, 506, 479, 478, 620 and 618 nm with CIE color coordinates of (0.29, 0.60), (0.27, 0.61), (0.13, 0.37), (0.14, 0.35), (0.67, 0.33) and (0.67, 0.33), respectively. The quantum chemical calculation shows that their emitting light is primarily from 3LC π−π* states of the cyclometalated ligand. Electroluminescent devices with dual light-emitting layers were fabricated and exhibited mild efficiency roll-off. [ABSTRACT FROM AUTHOR]

• A new dinuclear holmium(III) complex was synthesized. • The Ho(III) complex exhibit highly hydrogen-bonded supramolecular structure. • The Ho(III) complex display slow magnetic relaxation and proton-conducting behavior. Multifunctional magnetic-electrical materials are highly interesting, such as proton-conductive lanthanide single-ion magnets (SIMs). Herein, we reported the synthesis, crystal structure, magnetic and electrical properties of a bifunctional binuclear holmium(III) complex, [Ho 2 (H 2 dobdc)(H 2 O) 14 ]·(H 2 dobdc) 2 ·8H 2 O (Ho 2 , H 4 dobdc = 2,5-dioxodo-1,4-benzenedicarboxylate), which was constructed by a hydroxy‑functionalizd dicarboxybenzene and holmium(III) ions. Interestingly, single-crystal X-ray diffraction analysis reveals a highly hydrogen-bonded supramolecular structure and highly oxygenated site were formed within the complex. Magnetic measurements indicate the complex exhibits filed-induced slow magnetic relaxation property. Additionally, the impedance spectroscopy measurements show the complex also exhibits humidity- and temperature-dependent proton conduction behaviour via the Grotthus mechanism. These results support a proton-conductive holmium(III) single-ion magnet of Ho 2. This work not only provides the first bifunctional HoIII complexes showing slow magnetic relaxation and proton-conducting behaviour but also a supramolecular way for advanced magnetic-electrical systems linking slow magnetic relaxation with unique proton conducting behaviour exploiting a possible cooperative behaviour. A dinuclear holmium(III) complex with a highly hydrogen-bonded supramolecular structure was reported to show field-induced slow magnetic relaxation and proton-conducting behavior. [Display omitted] [ABSTRACT FROM AUTHOR]

Deciphering sedimentary provenance in the Okinawa Trough (OT) is vital for understanding the dispersal system from source to sink and the paleoenvironmental evolution in the East China Sea (ECS). Sources include the Huanghe, Changjiang, and Taiwan rivers, as well as the ECS shelf; however, there is controversy over which source has dominated sediment supply since the last deglaciation, and how the tidal currents, shelf circulation, and Kuroshio Current (KC) has controlled the sediment transport. Here, we present a high-resolution record of grain size and clay minerals over the last 14.3 kyrs in an AMS 14C dated piston core from the middle OT. We use these data to reconstruct changes in the KC, identify the provenance of fine-grained sediment, and unravel the impact of paleoenvironmental factors on these provenance changes. A grain size component of 15.6–31.3 μm was extracted to reconstruct the KC changes. These data show that the KC strengthened sharply until 10.2 ka, then kept strong and stable during the Holocene. Clay mineral assemblages indicate that the sediment was mainly derived from the ECS shelf between 14.3 and 8.6 ka, then from the Taiwan rivers after 8.6 ka. The shelf sediment was eroded and transported by intense tidal currents. Taiwan river sediment became the dominant source due to the development of Taiwan Warm Current rather than the strengthening of KC. The ratio of smectite and kaolinite to illite and chlorite content indicates that the sediment contribution from the Huanghe (old Huanghe delta) and Changjiang rivers increased from 7.6 to 5.0 ka and from 3.2 ka to the present. This increase is attributed to the strengthening of East Asian winter monsoon and the consequent intensification of cross-shelf circulation. • Sediment source changed from East China Sea shelf to Taiwan rivers at 8.6 ka. • Tidal reworking controls shelf sediment supply during the last deglaciation. • Taiwan Warm Current induces early Holocene provenance change rather than Kuroshio. • Winter monsoon enhances Huanghe and Changjiang supply at 7.6–5.0 ka and 3.2–0 ka. [ABSTRACT FROM AUTHOR]

Remotely operated vehicle (ROV) observations have recently revealed seep dolomite deposits covering the seafloor on Middle Dongsha of the South China Sea (SCS). Spurred by these findings, we studied the mineralogical and geochemical properties to examine the seep dolomite's origin, precipitation mechanism, and formation environment. These carbonates mainly comprise dolomite (from 64 to 84 wt%), followed by small amounts of calcite (from 1 to 3 wt%), locally containing magnesite (∼4 wt%), and goethite (∼14 wt%). Extensively developed mineralized cells containing high Mg and Ca contents found in chimneys imply that microbially-mediated processes probably participated in the reactivation of dolomite precipitation. The moderate and concentrated δ13C values (from −36.64 to −39.16‰, V-PDB) indicated that the carbon in carbonates was mainly derived from thermogenic methane. The methane fluids most likely ascended beneath the volcaniclastic unit and inherited enriched positive Eu anomalies due to fluid–rock interactions during their seepage along tectonic faults to the seafloor. The δ18O values (4.2–4.8‰, V-PDB) of carbonate suggested that an 18O-depleted fluid was involved in carbonate precipitation. The high total Rare-Earth Element contents (ΣREE) of seep carbonates varied from 61 ppm to 92 ppm, reflecting the chemical composition of surrounding pore waters at the time of carbonate precipitation, exhibiting less mixing with seawater. It may also indicate higher alkalinity and pH of the pore water. Although the sea-like REE patterns (HREE-enriched, negative Ce anomalies) are not caused by seawater, they may be due to the complexation competition between humic acid (HA) and carbonate for REE at high pore-water alkalinity and high CO 3 2− concentrations. This is consistent with the dolomite chimney pointing toward a formation environment in relatively deep sediments, in particular, close to the sulfate-methane interface in sediments, where the bicarbonate concentration reaches its maximum due to AOM. Moderate Mo and no U enrichments appeared in the carbonates, suggesting a relatively lower intensity of methane seepages with relatively reduced AOM rates. The wide range of (Mo/U) EF values and U–Mo covariation indicates the very dynamic AOM rate (slow to moderate) and redox conditions (mostly suboxic–anoxic, occasionally sulfidic conditions) during carbonate formation due to episodically changing seepage activity. [Display omitted] • Ancient cold seep chimneys in the M-Dongsha area contain dolomite as a dominant carbonate phase. • REE patterns reflect a higher alkalinity and pH of pore waters. • Mo-U element compositions indicates lower intensity seepages, dynamic AOM rate and environment. • Formed in a semi-closed microbially-mediated sediments environment. [ABSTRACT FROM AUTHOR]

• Complexes Ir1a, Ir1b, Ir2a and Ir2b possess four-membered Ir-N-C N chelating ring. • These complexes exhibit pure-green and pure-red phosphors in CH 2 Cl 2 solution. • The OLEDs exhibit high electroluminescent properties and mild efficiency roll-off. Herein four novel iridium(III) complexes (tfpmd) 2 Ir(dpppy) (Ir1a , tfpmd = 2-(4-(trifluoromethyl) phenyl) pyrimidine, dpppy = P ,P-diphenyl-N-(pyridin-2-yl)phosphinic amide), (tfpmd) 2 Ir(dppq) (Ir1b , dppq = P ,P-diphenyl-N-(quinolin-2-yl)phosphinic amide), (tfpqz) 2 Ir(dpppy) (Ir2a , tfpzq = 4-(4-(trifluoromethyl) phenyl) quinazoline) and (tfpqz) 2 Ir(dppq) (Ir2b) were synthetized, and their structures, opto-physical, and electro-chemical properties were investigated in detail. The crystal structure shows that these complexes exhibit pseudo-octahedral geometry around iridium atom coordinated by C, N atoms from cyclometalated and ancillary ligands. Interestingly, two coordinated nitrogen atoms from the ancillary ligand form an unusual quaternary ring with the central iridium ion. Ir1a and Ir1b emit pure-green light with Commission Internationale de L'Eclairage (CIE) color coordinates of (0.25, 0.67) and (0.22, 0.67), respectively, in CH 2 Cl 2 solution. With the increase of the degree of conjugation of the cyclometalated ligand from tfpmd to tfpqz, the luminescence of complexes Ir2a and Ir2b is greatly red-shifted, and pure-red emission with CIE coordinates of (0.66, 0.34) and (0.66, 0.34), respectively, is obtained. The photophysical behaviors were reasonably explained by quantum chemical calculations. The calculation results shows that their emission is ascribed to the mixed 3MLCT (metal-ligand charge transfer, dπ(Ir)→π*(cyclometalated ligand)) and 3LLCT (ligand-ligand charge transfer, π(ancillary ligand)→π*(cyclometalated ligand)) states. Owing to their good thermal and electrochemical stabilities, organic light emitting diode (OLED) devices with dual-emitting layer structure and a space interlayer were fabricated and exhibited high electroluminescent properties and mild efficiency roll-off (14%-21%). [Display omitted] [ABSTRACT FROM AUTHOR]

Geochemistry of iron and trace metals in seep carbonates and its dependence on anaerobic oxidation of methane (AOM)-driven diagenesis in cold seeps are not well documented. Here we characterize geochemistry of Fe and trace metals in carbonate nodules collected at an active cold seep in the middle Okinawa Trough (OT) impacted by hydrothermal plumes. The carbonate nodules in the studied core are dominated by aragonite even at sulfate-low core bottom. Most aragonite at the core bottom may have formed much earlier close to the seafloor under high sulfate concentration. Additionally, porewater at the depth may not be developed to a condition for the formation of calcite dominating over aragonite due to constant downward replenishment of sulfate across through shallow SMTZ (40 cm below sediment surface). As indicated by δ13C and δ18O of the carbonates, anaerobic oxidation of thermogenic methane from gas hydrate dissociation is the dominant fluid source for carbonate precipitation. It can be inferred from the existence of vivianite that Fe reduction coupled to AOM (Fe-AOM) may have ever been prevalent at the hydrothermal Fe-impacted seep site. Enhanced inputs of Mo, Co, Cu, Ni, and Zn associated with hydrothermal Fe-oxyhydroxides-organic colloids is the main source for their high enrichment in the carbonate nodules, and clay minerals and AOM-related microbial organics may have played an important role in their partitioning in the nodules. Uranium enrichment in the carbonate nodules is mainly through enhanced U delivery associated with Fe-oxyhydroxides-scavenged organic colloids and additional U enrichment induced by U(VI) reduction. U(IV) incorporation into carbonate lattices dominates U partitioning in the carbonate nodules over the upper 60 cm of the seep sediments, but the incorporation is substantially dampened at depth due to an increase in concentration of dissolved inorganic carbon, which consequently may have rendered U(IV) adsorption on clay minerals as the important U sink in the nodules. Our results suggest that the exceptional enrichments of Co, Cu, Ni, Zn, Mo, and U in seep carbonates may be used as a paleo-proxy to differentiate cold-seep carbonates whose formation has been co-impacted by hydrothermal plumes. • Aragonite is the dominant carbonate mineral even at sulfate-poor core bottom. • Carbonate formation is related to AOM and hydrate dissociation. • Hydrothermal Fe input enhances trace metal enrichment in carbonate nodules. • Clays and AOM-microbial organics play an important role in trace metal partitioning. [ABSTRACT FROM AUTHOR]

Four co-edge rhomboid [Ln 4 (μ 3 -OH) 2 ]-based 1D chainlike LnCPs were synthesized based on orotic acid. The Gd-containing complex displays a large MCE of −Δ S m max = 37.11 J kg−1 K−1, and the Eu- and Tb-based polymers exhibit characteristic Ln(III) luminescence. [Display omitted] • Four isostructural 1D LnCPs with rhomboid [Ln 4 (μ 3 -OH) 2 ]-based chainlike structure were obtained hydrothermally. • The Gd(III)-containing polymer displays a large MCE with − Δ S m max value of 37.11 J kg−1 K−1. • The Eu- and Tb-based polymers exhibit characteristic Eu(III)/Tb(III) luminescence. Four isostructural lanthanide coordination polymers with orotic acid (H 3 OA) as building ligand, {[Ln(HOA)(μ 3 -OH)(H 2 O) 2 ]·H 2 O} n (Ln = Eu (1); Gd (2); Tb (3); Dy (4)), were synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analyses demonstrate that complexes 1 – 4 have an one-dimensional (1D) chainlike structure consisting of rhomboid [Ln 4 (μ 3 -OH) 2 ] unit and HOA2- linker. Magnetic studies indicate that 2 displays a large magnetocaloric effect with magnetic entropy value of 37.11 J kg−1 K−1 at 2.0 K for Δ H = 7.0 T. This is a considerable value among the reported molecular magnetic coolants, and has a great application potential in the field of ultra-low temperature refrigeration. In addition, the solid-state photophysical properties of 1 and 3 exhibit obvious characteristic Eu(III) and Tb(III) photoluminescence emission in the visible region, suggesting that Eu- and Tb-based luminescence were sensitized effectively by the energy transfer from the ligand to the metal centers. [ABSTRACT FROM AUTHOR]

• A rare zigzag [Fe 2 Co 2 ] cluster was constructed by [(Tp*)Fe(CN) 3 ]− anions and tetrapyridophenazine ligand. • Dynamic magnetic switching was observed between the hydrated and dehydrated phases. • Field-induced single-molecule magnet behavior was evidenced in the dehydrated complex. A rare zigzag cyanide-bridged tetranuclear complex, {[(Tp*)FeIII(CN) 3 ] 2 [CoII(tphz) 1/2 (SCN)(MeOH)] 2 }·4H 2 O (1 ·4H 2 O) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate, tphz = tetrapyridophenazine) was successfully isolated and characterized structurally and magnetically. Single-crystal structural analysis indicates the Fe3+ and Co2+ ions are linked by cyanides while the inverse two Co2+ are bridged by the pyrazine of tphz. Magnetic studies for 1 ·4H 2 O revealed the ferromagnetic coupling (J Fe Co = +3.2 cm−1) between the Fe3+ and Co2+ ions and antiferromagnetic interaction (J Co Co = −2.7 cm−1) between the Co2+ ions of the cluster. After the release of crystallized water molecules, however, the magnetic behaviors were drastically tuned indicated by the notable changes in the magnetic couplings for FeIII CoII (J Fe Co = +3.9 cm−1) and CoII CoII (J Co Co = −3.5 cm−1). Reduced magnetization reveals the uniaxial magnetic anisotropy of the dehydrated molecule with the zero-field splitting parameter D = −10.3 cm−1. Additionally, field-supported single-molecule magnet behavior was observed with the effective energy barrier U eff = 38.2 K, making complex 1 the first example of a zigzag Fe 2 Co 2 single-molecule magnet. This work provides not only a rare dynamic switching molecular complex but also highlights the important influence of guest water molecules in magnetic behaviors. Dehydration-actuated single-molecule magnet behavior was observed in a rare cyanide-bridged [Fe 2 Co 2 ] cluster featuring a zigzag structure. [Display omitted] [ABSTRACT FROM AUTHOR]