Gold Nanoclusters whose Photoluminescent Properties are Dynamically Tunable by Modulating the Assembly Pathway Complexity.

Modulating the assembly pathway is an indispensable strategy for optimizing the performance of optical materials. However, implementing this strategy is nontrivial for metal nanocluster building blocks, due to the limited functional modification of nanoclusters and complexity of their emission mechanism. In this report, we demonstrate that a gold nanocluster modified by 4,6-diamino-2-pyrimidinethiol (DPT-AuNCs) self-assembles into two distinct aggregation structures in methanol (MeOH)/water mixed solvent, thus exhibiting pathway complexity. Kinetic studies show that DPT-AuNCs firstly assembles into non-luminescent nanofibers (kinetically controlled), which further transforms into strongly luminescent microflowers (thermodynamicallycontrolled). In-depth analysis of the assembly mechanism reveals that the transformation of aggregation structures involves the disassembly of nanofibers and a subsequent nucleation-growth process. Temperature-dependent photoluminescence (PL) spectroscopy and infrared (IR) measurements reveal that inter-cluster hydrogen bonding bridged by solvent molecules and C-H···π interaction are the key factors for emission enhancement. The photoluminescent property of DPT-AuNCs can be controlled by varying the cosolvent in water, enabling DPT-AuNCs to distinguish different kind of alcohols, particularly the isomerism n-propanol (NPA) and isopropanol (IPA). Additionally, he addition of seeds effectively regulate the assembly kinetics of DPT-AuNCs. This study advances our understanding of assembly pathways and improves the luminescent performance of nanoclusters (NCs).

Polymer-Enabled Assembly of Au Nanoclusters with Luminescence Enhancement and Macroscopic Chirality.

The construction of macroscopic chiral luminescent aggregates with well-defined structures not only contributes to the development of functional materials but also has significant implications for analyzing chiral transfer and amplification in biological systems and self-assembly systems. Meanwhile, achieving water-soluble chiral metal nanoclusters (NCs) with high photoluminescence (PL) intensity through a convenient method remains a challenge. Herein, we reported the enhanced luminescence of gold nanoclusters stabilized by D-/L-penicillamine (D-/L-AuNCs) induced by poly(allylamine hydrochloride) (PAH) through supramolecular self-assembly strategies. FT-IR spectra and zeta potential measurements revealed that supramolecular assembly was driven by the synergistic effect of hydrogen bonds and electrostatic interactions, which effectively limited the intramolecular vibration and rotation of the ligand and reduced nonradiative relaxation, thus improving the luminescence properties of nanoclusters. Interestingly, during the slow solvent evaporation process, chiral entanglement of assemblies was enhanced, forming macroscopic wheat-shaped superstructures. This study enriches the understanding of the self-assembly mechanism of nanoclusters and provides a pathway for constructing NC-based chiroptical materials.

ß-Sitosterol Suppresses Lipopolysaccharide-Induced Inflammation and Lipogenesis Disorder in Bovine Mammary Epithelial Cells.

ß-sitosterol, a natural plant steroid, has been shown to promote anti-inflammatory and antioxidant activities in the body. In this study, ß-sitosterol was used to protect against lipopolysaccharide (LPS)-induced cell damage in bovine mammary epithelial cells, which are commonly studied as a cell model of mammary inflammatory response and lipogenesis. Results showed that treatment with a combination of LPS and ß-sitosterol significantly reduced oxidative stress and inflammation, while increasing the expression of anti-apoptotic proteins and activating the hypoxia-inducible factor-1(HIF-1α)/mammalian target of rapamycin(mTOR) signaling pathway to inhibit apoptosis and improve lipid synthesis-related gene expression. Our finding suggests that ß-sitosterol has the potential to alleviate inflammation in the mammary gland.

Effects of dietary grape pomace on the intestinal microbiota and growth performance of weaned piglets.

Grape pomace (GP) is an abundant by-product from wine production and is rich in phenolic compounds, unsaturated fatty acids, dietary fibre and beneficial bacteria. In this study, weaned piglets were fed a basic diet supplemented with 5% GP for 4 weeks. Compared with those in the control (CON) group, it was found that the proportion of Lactobacillus delbrueckii, Olsenella umbonata and Selenomonas bovis in the caecum and the villus height and villus height/crypt depth ratio (VCR) of the jejunum were both significantly increased in the GP group (p < 0.05). Meanwhile, at the mRNA expression level, several proinflammatory cytokines (IL-1ß, IL-8, IL-6 and TNF-α) were significantly downregulated (p < 0.05) in piglet caecal tissue, and the short-chain fatty acid receptors (GPR41 and GPR43) were not significantly upregulated. In contrast, the levels of IgG was significantly increased (p < 0.05) in the sera of weaned piglets in the GP group. However, no difference in growth performance between the two groups of piglets was detected. These results show that GP had no adverse effects on the growth performance of piglets, but GP can promote the content of some beneficial bacteria in the caecum; this effect is conducive to improving the disease resistance potential of piglets.

Effect of all-trans retinoic acid on casein and fatty acid synthesis in MAC-T cells.

OBJECTIVE: Caseins and fatty acids of milk are synthesized and secreted by the epithelial cells of the mammary gland. All-trans retinoic acid (ATRA), an active metabolite of vitamin A, has been shown to promote mammary development. This study was conducted to determine the effect of ATRA on casein synthesis and fatty acid composition in MAC-T cells. METHODS: MAC-T cells were allowed to differentiate for 4 d, treated with ATRA (0, 1.0, 1.5, and 2.0 µM), and incubated for 3 d. We analyzed the fatty acid composition, the mRNA expression of casein and fatty acid synthesis-related genes, and the phosphorylation of casein synthesis-related proteins of MAC-T cells by gas chromatography, quantitative polymerase chain reaction, and western blotting, respectively. RESULTS: In MAC-T cells, ATRA increased the mRNA levels of αS1-casein and ß-casein, janus kinase 2 (JAK2) and E74-like factor 5 of the signal transducer and activator of transcription 5 ß (STAT5-ß) pathway, ribosomal protein S6 kinase beta-1 (S6K1) and eukaryotic translation initiation factor 4E binding protein 1 of the mammalian target of rapamycin (mTOR) pathway, inhibited the mRNA expression of phosphoinositide 3-kinase and eukaryotic initiation factor 4E of the mTOR pathway, and promoted the phosphorylation of STAT5-ß and S6K1 proteins. Additionally, ATRA increased the de novo synthesis of fatty acids, reduced the content of long-chain fatty acids, the ratio of monounsaturated fatty acids to saturated fatty acids (SFA), the ratio of polyunsaturated fatty acids (PUFA) to SFA, and the ratio of ω-6 to ω-3 PUFA. The mRNA levels of acetyl-CoA carboxylase 1, fatty acid synthase, lipoprotein lipase, stearoyl-CoA desaturase, peroxisome proliferator-activated receptor gamma, and sterol regulatory element-binding protein 1 (SREBP1) were enhanced by ATRA. CONCLUSION: ATRA promotes the synthesis of casein by regulating JAK2/STAT5 pathway and downstream mTOR signaling pathway, and it improves the fatty acid composition of MAC-T cells by regulating SREBP1-related genes.

L-Arginine and N-carbamoylglutamic acid supplementation enhance young rabbit growth and immunity by regulating intestinal microbial community.

OBJECTIVE: An experiment was conducted to determine the effects of L-arginine (L-Arg) and N-carbamoylglutamic acid (NCG) on the growth, metabolism, immunity and community of cecal bacterial flora of weanling and young rabbits. METHODS: Eighteen normal-grade male weanling Japanese White Rabbits (JWR) were selected and randomly divided into 6 groups with or without L-Arg and NCG supplementation. The whole feeding process was divided into weanling stage (Day 37 to 65) and young stage (Day 66 to 85). The effects of L-Arg and NCG on the growth, metabolism, immunity and development of the ileum and jejunum were compared via nutrient metabolism experiments and histological assessment. The different communities of cecal bacterial flora affected by L-Arg and NCG were assessed using high-throughput sequencing technology and bioinformatics analysis. RESULTS: The addition of L-Arg and NCG were able to enhance the growth of weanling and young rabbit by increasing the nitrogen metabolism, protein efficiency ratio, and biological value, as well as feed intake, daily weight gain. Both L-Arg and NCG were able to increase the concentration of IgA, IgM, and IgG. NCG was superior to L-Arg in promoting intestinal villus development by increasing villus height and V/C index, reducing the crypt depth. The effects of L-Arg and NCG on the cecal bacterial flora were mainly concentrated in different genera, including Parabacteroides, Roseburia, dgA-11_gut_group, Alistipes, Bacteroides, and Ruminococcaceae_UCG-005. These bacteria function mainly in amino acid transport and metabolism, energy production and conversion, lipid transport and metabolism, recombination and repair, cell cycle control, cell division, and cell motility. CONCLUSION: L-Arg and NCG have promotional ability on the growth and immunity of weanling and young Japanese White Rabbits, as well as their effects on the jejunum and ileum villi. L-Arg and NCG have different effects in the promotion of nutrient utilization, relieving inflammation and enhancing adaptability through regulating microbial community.

Amphiphilicity Regulation of AgI Nanoclusters: Self-Assembly and Its Application as a Luminescent Probe.

Research on the self-assembly of various amphiphilic molecules is a relatively new research area and of great significance. However, new kinds of metal-nanocluster (NC)-based amphiphilic molecule have rarely been explored. Herein, hydrophobic cation 1-hexadecyl-3-methylimidazolium (C16 mim+ ) was chosen to modify hydrophilic (NH4 )6 [Ag6 (mna)6 ] (Ag6 -NCs, H2 mna=2-mercaptonicotinic acid) and Ag6 @C16 mim-NCs were obtained. Ag6 @C16 mim-NCs displayed thermotropic liquid crystal and thermofluorescent properties. Moreover, the Ag6 @C16 mim-NCs exhibits benign amphiphilicity, and it can self-assemble into ordered nanosheets and nanorods through aggregation in water/dimethyl sulfoxide (DMSO) binary solvent mixtures, whereas single Ag6 -NCs do not. Meanwhile, the Ag6 @C16 mim-NCs also displays aggregation-induced emission properties owing to the restriction of intramolecular vibrations of the capping ligands. Furthermore, the luminescent aggregates could detect arginine selectively with the detection limit at 28 µm. This study introduces a new kind of metal-NC-based amphiphilic molecule in a supramolecular self-assembly field, and they have potential to be used as optical materials in applied research.

Zearalenone induces apoptosis in bovine mammary epithelial cells by activating endoplasmic reticulum stress.

Zearalenone (ZEA) is a common mycotoxin produced by fungi within the genus Fusarium. However, few studies have examined the direct effects of the toxin on the mammary glands. In the present study, the effects of ZEA treatment on bovine mammary epithelial cells (MAC-T) from dairy cows were investigated. The cells were treated with different concentrations of ZEA to evaluate the effect of the toxin on cell viability, intracellular reactive oxygen species (ROS) concentrations, mitochondrial membrane potential, endoplasmic reticulum (ER) stress, and the expression of apoptosis-related genes. The results indicated that different concentrations (5, 10, 15, 20, 25, 30, 50, 60, or 100 µM) of ZEA were able to inhibit growth of MAC-T cells. After exposing the MAC-T cells to 30 µM ZEA, compared with the control group, ROS levels increased, mitochondrial membrane potential decreased, and mRNA expression of the ER-specific stress-related genes GRP78, HSP70, ATF6, EIF2A, ASK1, and CHOP was upregulated in the ZEA-treated group. Further, we analyzed the increase in apoptotic rate by flow cytometry. At the mRNA level, compared with the control group, the expression of the apoptosis-promoting gene BAX was increased in the ZEA-treated group, the expression of the inhibitory gene BCL2 decreased, and the expression of the gene CASP3 increased. We observed a significant increase in caspase-3 activity in ZEA-treated MAC-T cells. Furthermore, the apoptotic rate of the cells in the ZEA group treated with 4-phenylbutyric acid (ER stress inhibitor) decreased and the mRNA expression levels of ER stress markers GRP78 and CHOP decreased. Compared with the ZEA treatment group, the mRNA expression level of the apoptosis-related gene BAX was decreased and the expression level of BCL2 was increased in the ZEA + 4-phenylbutyric acid cotreatment group. These findings indicate that ZEA-induced ER stress increases apoptosis in MAC-T cells. The treatment of MAC-T cells with ZEA reduced cell viability, increased ROS content, decreased mitochondrial membrane potential, increased ER stress marker expression, and induced apoptosis.

Deoxynivalenol induces oxidative stress, inflammatory response and apoptosis in bovine mammary epithelial cells.

Deoxynivalenol (DON) is a toxic secondary metabolite produced by Fusarium graminearum. It is one of the most common feed contaminants that poses a serious threat to the health and performance of dairy cows. This study investigated the in vitro cytotoxicity of DON on bovine mammary epithelial cells (MAC-T). DON at different concentrations (0.25, 0.3, 0.5, 0.8, 1 or 2 µg/ml) inhibited the growth of MAC-T cells after 24 hr of exposure (p < .001). DON at 0.25 µg/ml increased lactate dehydrogenase (LDH) leakage (p < .05); decreased glutathione (GSH) levels (p < .001), total superoxide dismutase (T-SOD) activity and total antioxidant capacity (T-AOC; p < .01); and increased malondialdehyde (MDA) concentration (p < .01) in MAC-T cells after 24 hr of exposure. We also observed that DON increased reactive oxygen species (ROS) levels in cells incubated for 9, 15 and 24 hr (p < .001). DON at 0.25 µg/ml triggered oxidative damage in MAC-T cells. Furthermore, it induced an inflammatory response in the cells incubated for 9, 15 and 24 hr (p < .05) by increasing the mRNA expression levels of nuclear factor kappa B, myeloid differentiation factor 88 (MyD88), tumour necrosis factor-α (TNF-α), interleukin-1ß (IL-1ß), IL-6, cyclooxygenase-2 and IL-8. We further examined the effect of DON on apoptosis. DON prevented normal proliferation of MAC-T cells by blocked cell cycle progression in 24 hr (p < .001). In addition, the apoptosis rate measured using annexin V-FITC significantly increased (p < .05) with increase in the mRNA expression level of Bax (p < .01) and increase in the Bax/Bcl-2 ratio (p < .01) in cells incubated for 24 hr. In summary, DON exerts toxic effects in MAC-T cells by causing oxidative stress, inducing an inflammatory response, affecting cell cycle and leading to apoptosis.

Ionic Self-Assembly of a Giant Vesicle as a Smart Microcarrier and Microreactor.

Giant vesicles (1-10 µm) were constructed via a facile ionic self-assembly (ISA) strategy using an anionic dye Acid Orange II (AO) and an oppositely charged ionic-liquid-type cationic surfactant 1-tetradecyl-3-methylimidazolium bromide (C14mimBr). This is the first report about preparing giant vesicles through ISA strategy. Interestingly, the giant vesicle could keep the original morphology during the evaporation of solvent and displayed solid-like properties at low concentration. Moreover, giant vesicles with large internal capacity volume and good stability in solution could also be achieved by increasing the concentrations of AO and C14mimBr which contributed to the increase of the other noncovalent cooperative interactions. In order to facilitate comparison, a series of parallel experiments with similar materials were carried out to investigate and verify the driving forces for the formation of these kinds of giant vesicles by changing the hydrophobic moieties or the head groups of the surfactants. It is concluded that the electrostatic interaction, hydrophobic effect and π-π stacking interaction play key roles in this self-assembly process. Importantly, the giant vesicles can act as a smart microcarrier to load and release carbon quantum dot (CQD) under control. Besides, the giant vesicles could also be applied as a microrector to synthesize monodispersed Ag nanoparticles with diameter of about 5-10 nm which exhibited the ability to catalyze reduction of 4-nitroaniline. Therefore, it is indicated that our AO/C14mimBr assemblies hold promising applications in the areas of microencapsulation, catalyst support, and lightweight composites owing to their huge sizes and large microcavities.

A systematic study of the effect of molecular weights of polyvinyl alcohol on polyvinyl alcohol-graphene oxide composite hydrogels.

Polyvinyl alcohol (PVA) hydrogels have been proposed for use as promising biomaterials in biomedical and tissue engineering, and graphene oxide (GO) has been recognized as a unique two-dimensional building block for various graphene-based supramolecular architectures. In this article, we systematically studied the influence of three kinds of PVA with different molecular weights on the interaction between PVA and GO. Moreover, the effects of PVA on the gelation of GO were also investigated. The native PVA hydrogel, as well as PVA-GO hybrid hydrogels, have been thoroughly characterized by the phase behavior study and various techniques including field emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and rheological measurements. It can be seen that with the increase of the molecular weight of PVA, the addition of GO can effectively promote the gelation of PVA which can be reflected by a decrease of the critical gel concentration (CGC) for PVA-GO hydrogels. Dye adsorption experiments indicate that the toxic dye, i.e., methylene blue (MB), was efficiently entrapped in the PVA-GO xerogels. It is also demonstrated that the gelation of PVA and GO composites can be promoted by different supramolecular interactions, including hydrogen bonding and electrostatic interaction. This work indicates that the PVA-GO composite is a good candidate for preparing "super" and "smart" hydrogels and will enable further studies on the supramolecular chemistry of PVA, graphene and its derivatives.

Comparative study of n-dodecyl tetraethylene monoether lyotropic liquid crystals incorporated with graphene and graphene oxide.

Two kinds of carbon materials, i.e., graphene and graphene oxide (GO), were successfully incorporated into a lyotropic liquid crystal (LLC) matrix formed by n-dodecyl tetraethylene monoether (C12E4). The properties of graphene-C12E4 and GO-C12E4 LLC composites were characterized by UV-vis absorption, transmission electron microscopy (TEM) observations, polarized optical microscopy (POM) observations, small-angle X-ray scattering (SAXS) and rheological measurements. SAXS results indicate that both graphene and GO are well-dispersed in the C12E4 LLC matrix and some interactions occur between the C12E4 LLC matrix and graphene (or GO) sheets. Moreover, it is demonstrated that graphene interacts with the hydrophobic part of C12E4 LLC while GO mainly interacts with the hydrophilic part of C12E4 LLC because of the different properties of graphene and GO. Integration of graphene and GO into C12E4-PEG systems by a spontaneous phase separation method reveals the different interaction mechanisms of graphene and GO with C12E4 LLC. It can be concluded that the mechanical and electrical properties of the C12E4 LLC have been largely improved by the incorporation of graphene and GO, which opens the door for wide applications in nanotechnology, electrochemical and biochemical areas.

Ordered carbon nanotubes-n-dodecyl tetraethylene monoether liquid crystal composites through phase separation induced by poly(ethylene glycol).

Carbon nanotubes (CNTs) were incorporated into a lyotropic liquid crystal (LLC) matrix at room temperature through spontaneous phase separation. The phase separation process occurred in n-dodecyl tetraethylene monoether (C12E4) solutions induced by the hydrophilic polymer, poly(ethylene glycol) (PEG). It was found that the molecular weight of PEG has a significant effect on the CNTs-C12E4 system, which not only influences the phase behavior of the system but also changes the properties of the CNTs-LLC composites. Polarized optical microscopy (POM) images, combined with small-angle X-ray scattering (SAXS) results, indicate that CNTs incorporate within the layers of the lamellar LLCs without destroying the structure of LLCs. Moreover, UV-vis absorption, Raman spectra and rheological measurements were performed to investigate the characteristic properties of the CNTs-LLC composites. This study not only gives a more comprehensive understanding of polymer-induced phase separation, but also expands the potential uses of CNTs-LLC composites in nanotechnology.

Optimization of Extraction of Four Components from Radix Scrophulariae with Natural Deep Eutectic Solvents and Evaluation of Extract's Antioxidant Activity.

In this research, eight natural deep eutectic solvents (NaDESs) consisting of food-grade ingredients were screened for the extraction of four bioactive compounds (acteoside, cinnamic acid, angoroside C and harpagoside) from radix scrophulariae (RS). Among these NaDESs, Proline-Glycerol NaDES with higher comprehensive score was selected. The Criteria Importance Through Intercriteria Correlation (CRITIC) was applied to calculate the information entropy and the weight of indexes, and figured out a comprehensive score. The weights of acteoside, cinnamic acid, angoroside C and harpagoside were 0.369, 0.172, 0.241 and 0.218, respectively. Response surface methodology (RSM) mathematical model was used to optimize the extraction parameters. The optimal extraction parameters were as follows: extraction time with 42.21 min, NaDES concentration with 52.89%, solid-to-liquid ratio with 1 : 37.05 g/mL and the predicted value of comprehensive score was 0.885. Under the optimal condition, the comprehensive score was 0.903 ± 0.005. Finally, the antioxidant activity experiment revealed that the 1,1-Diphenyl-2-picrylhydrazyl · radical scavenging activity and hydroxyl radical scavenging activity of the extract at 2.0 mg/mL and 1.5 mg/mL were approximately equal to those of ascorbic acid, respectively. The results showed that the extraction condition optimized by RSM combined with CRITIC was reasonable and dependable, and the extract of radix scrophulariae exhibited good antioxidant activity.

Lithium Chloride Promotes Endogenous Synthesis of CLA in Bovine Mammary Epithelial Cells.

Although conjugated linoleic acid (CLA) can promote human health, its content in milk is insufficient to have a significant impact. The majority of the CLA in milk is produced endogenously by the mammary gland. However, research on improving its content through nutrient-induced endogenous synthesis is relatively scarce. Previous research found that the key enzyme, stearoyl-CoA desaturase (SCD) for the synthesis of CLA, can be expressed more actively in bovine mammary epithelial cells (MAC-T) when lithium chloride (LiCl) is present. This study investigated whether LiCl can encourage CLA synthesis in MAC-T cells. The results showed that LiCl effectively increased SCD and proteasome α5 subunit (PSMA5) protein expression in MAC-T cells as well as the content of CLA and its endogenous synthesis index. LiCl enhanced the expression of proliferator-activated receptor-γ (PPARγ), sterol regulatory element-binding protein 1 (SREBP1), and its downstream enzymes acetyl CoA carboxylase (ACC), fatty acid synthase (FASN), lipoprotein lipase (LPL), and Perilipin 2 (PLIN2). The addition of LiCl significantly enhanced p-GSK-3ß, ß-catenin, p-ß-catenin protein expression, hypoxia-inducible factor-1α (HIF-1α), and downregulation factor genes for mRNA expression (P < 0.05). These findings highlight that LiCl can increase the expression of SCD and PSMA5 by activating the transcription of HIF-1α, Wnt/ß-catenin, and the SREBP1 signaling pathways to promote the conversion of trans-vaccenic acid (TVA) to the endogenous synthesis of CLA. This data suggests that the exogenous addition of nutrients can increase CLA content in milk through pertinent signaling pathways.

Integrated Microbiome and Metabolomics Analysis of the Effects of Dietary Supplementation with Corn-Steep-Liquor-Derived Candida utilis Feed on Black Pigs.

In this experiment, glucose master liquor and corn steep liquor were used as carbon and nitrogen sources, and Candida utilis was used as a strain to ferment yeast feed. The OD value and number of yeast cells were used as response values to optimize the medium components of the yeast feed through a response surface methodology. The optimal medium components were a glucose master liquor concentration of 8.3%, a corn steep liquor concentration of 1.2%, and a KH2PO4 concentration of 0.14%. Under this condition of fermentation, the OD value was 0.670 and the number of yeast cells was 2.72 × 108/mL. Then, we fed Candida utilis feed to Dongliao black piglets, and the effects of the yeast feed on the piglets' growth performance, fecal microbiota, and plasma metabolic levels were investigated through 16S rDNA sequencing and metabolomics. In total, 120 black piglets with an average initial weight of 6.90 ± 1.28 kg were randomly divided into two groups. One group was fed the basic diet (the CON group), and the other was supplemented with 2.5% Candida utilis add to the basic diet (the 2.5% CU group). After a pre-feeding period, the formal experiments were performed for 21 days. The results showed that the addition of Candida utilis to the diet did not affect growth performance compared with the control group. Meanwhile, no significant differences were observed in the serum biochemical indices. However, piglets in the 2.5% CU group had a significantly altered fecal microbiota, with an increased abundance of Clostridium_sensu_stricto_1, Lactobacillus, and Muribaculaceae_unclassified. Regarding the plasma metabolome, the 12 differential metabolites detected were mainly enriched in the histidine, tryptophan, primary bile acid, and caffeine metabolic pathways. Regarding the integrated microbiome-metabolome analysis, differential metabolites correlated with fecal flora to variable degrees, but most of them were beneficial bacteria of Firmicutes. Collectively, dietary Candida utilis feed had no adverse effect on growth performance; however, it played an important role in regulating fecal flora and maintaining metabolic levels.

Gold nanoclusters with enhanced near-infrared emission and its application as sensors for biological molecules.

Ultrasmall gold nanoclusters (NCs) have been engineered as a new kind of functional material due to their excellent photoluminescence properties. However, the synthesis of highly luminescent water-soluble nanoclusters with near-infrared (NIR) emission remains limited. Herein, we developed a pH-regulated strategy to facilitate the construction of self-assemblies with enhanced luminescence based on aggregation-induced emission (AIE) strategy. Using 2-mercaptobenzoic acid (MBA) as reductant and stabilizer, the original weakly luminescent AuNCs exhibited intense emission by adjusting pH controllably. The formation of compact organized nanostructures could effectively restrict the rotation and vibration of capping ligands by non-covalent interactions, which reduced the nonradiative relaxation from excited states and finally improved the emission properties of AuNCs. Moreover, the assemblies possess many intriguing features including bright NIR luminescence and excellent biocompatibility, which could be used as luminous probes in biological molecules sensing (tyrosinase (TYR) and dopamine (DA)) and promising candidates for cell imaging. This study provides a simple and feasible strategy for developing metal NCs-based smart optical materials in the field of bioscience.

Lithium Chloride Promotes Milk Protein and Fat Synthesis in Bovine Mammary Epithelial Cells via HIF-1α and ß-Catenin Signaling Pathways.

Lithium is one of the trace elements with many physiological properties, such as being anti-cancer, anti-viral, and anti-inflammatory. However, little is known about its effect on milk synthesis during lactation. Therefore, we selected different concentrations (5 mM, 10 mM, and 20 mM) of lithium chloride (LiCl) and assessed the effect of LiCl on bovine mammary epithelial (MAC-T) cells that underwent 4 days of differentiation induction. Moreover, we analyzed the effect of LiCl on the expression of genes related to milk fat and milk protein synthesis. Herein, LiCl (5-20 mM) significantly increased the expression of ß-casein, promoted mRNA expression and phosphorylated protein expression of the signal transduction molecule and activator of transcription 5ß (STAT5-ß), and inhibited mRNA and protein expression of suppressor of cytokine signaling 2 (SOCS2). In contrast, 5 and 10 mM LiCl significantly inhibited expression of SOCS3. LiCl at concentration of 5-20 mM enhanced phosphorylation level of mTOR protein; at 10 mM and 20 mM, LiCl significantly promoted expression and phosphorylation of downstream ribosomal protein S6 kinase beta-1 (S6K1) protein. Considering milk fat synthesis, mRNA expression of acetyl CoA carboxylase (ACC) and lipoprotein lipase (LPL) genes was considerably increased in the presence of LiCl (5-20 mM). Additionally, increased protein expression levels of stearoyl-CoA desaturase (SCD), peroxisome proliferator-activated receptor-γ (PPARγ), and sterol regulatory element-binding protein 1 (SREBP1) were observed at all LiCl concentrations tested. Subsequently, LiCl (5-20 mM) significantly promoted protein expression and phosphorylation of ß-catenin, while 10 mM and 20 mM of LiCl significantly promoted protein expression of hypoxia-inducible factor-1α (HIF-1α). Collectively, it has been shown that 10 mM LiCl can effectively activate HIF-1α, ß-catenin, and ß-catenin downstream signaling pathways. Conversely, at 10 mM, LiCl inhibited SOCS2 and SOCS3 protein expression through JAK2/STAT5, mTOR, and SREBP1 signaling pathways, improving synthesis of milk protein and fat. Therefore, LiCl can be used as a potential nutrient to regulate milk synthesis in dairy cows.

Enzyme coordination conferring stable monodispersity of diverse metal-organic frameworks for photothermal/starvation therapy.

The agglomeration of metal-organic frameworks (MOFs) has long been a problem, and achieving stable monodispersity in water remains a great challenge. This paper reports a universal strategy that functionalizes MOFs by using an endogenous bioenzyme namely glucose oxidase (GOx), to achieve stable water monodispersity, and integrates it as a highly efficient nanoplatform for cancer synergistic therapy. Phenolic hydroxyl groups in GOx chain confers robust coordination interactions with MOFs, which not only endows stable monodispersion in water, but also provides many reactive sites for further modification. Silver nanoparticles are uniformly deposited onto MOFs@GOx to achieve high conversion efficiency from near-infrared light to heat, resulting in an effective starvation and photothermal synergistic therapy model. In vitro and in vivo experiments confirm excellent therapeutic effect at very low doses without using any chemotherapeutics. In addition, the nanoplatform generates large amounts of reactive oxygen species, induces heavy cell apoptosis, and demonstrates the first experimental example to effectively inhibit cancer migration. Our universal strategy enables stable monodispersity of various MOFs via GOx functionalization and establishes a non-invasive platform for efficient cancer synergistic therapy.

Manipulating the Assembly of Au Nanoclusters for Luminescence Enhancement and Circularly Polarized Luminescence.

Au nanocluster (AuNCs)-based luminescent functional materials have attracted the interest of researchers owing to their small size, tractable surface modification, phosphorescence lifetime and biocompatibility. However, the poor luminescence quantum yield (QY) of AuNCs limits their practical applications. Herein, we synthesized a type of AuNCs modified by 4,6-diamino-2-mercaptopyrimidine hydrate (DPT-AuNCs). Furthermore, organic acids, i.e., citric acid (CA) and tartaric acid (TA), were chosen for co-assembly with DPT-AuNCs to produce AuNCs-based luminescent materials with enhanced emission. Firstly, it was found that CA could significantly enhance the emission of DPT-AuNCs with the formation of red emission nanofibers (QY = 17.31%), which showed a potential for usage in I- detection. The n···π/π···π interaction between the CA and the DPT ligand was proposed as crucial for the emission. Moreover, chiral TA could not only improve the emission of DPT-AuNCs, but could also transfer its chirality to DPT-AuNCs and induce the formation of circularly polarized luminescence (CPL)-active nanofibers. It was demonstrated that the CPL signal could increase 4.6-fold in a ternary CA/TA/DPT-AuNCs co-assembly system. This work provides a convenient way to build AuNCs-based luminescent materials as probes, and opens a new avenue for building CPL-active materials by achiral NCs through a co-assembly strategy.