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1.
Front Vet Sci ; 11: 1330693, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38645645

RESUMO

Bovine tuberculosis (bTB) is a chronic zoonotic disease caused by Mycobacterium bovis. A large number of cattle are infected with bTB every year, resulting in huge economic losses. How to control bTB is an important issue in the current global livestock economy. In this study, the original transcriptome sequences related to this study were obtained from the dataset GSE192537 by searching the Gene Expression Omnibus (GEO) database. Our differential gene analysis showed that there were obvious biological activities related to immune activation and immune regulation in the early stage of bTB. Immune-related biological processes were more active in the early stage of bTB than in the late. There were obvious immune activation and immune cell recruitment in the early stage of bTB. Regulations in immune receptors are associated with pathophysiological processes of the early stage of bTB. A gene module consisting of 236 genes significantly related to the early stage of bTB was obtained by weighted gene co-expression network analysis, and 18 hub genes were further identified as potential biomarkers or therapeutic targets. Finally, by random forest algorithm and logistic regression modeling, FCRL1 was identified as a representative mRNA marker in early bTB blood. FCRL1 has the potential to be a diagnostic biomarker in early bTB.

2.
Nat Commun ; 15(1): 3030, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38589464

RESUMO

On-surface synthesis provides tools to prepare low-dimensional supramolecular structures. Traditionally, reactive radicals are a class of single-electron species, serving as exceptional electron-withdrawing groups. On metal surfaces, however, such species are affected by conduction band screening effects that may even quench their unpaired electron characteristics. As a result, radicals are expected to be less active, and reactions catalyzed by surface-stabilized radicals are rarely reported. Herein, we describe a class of inter-molecular radical transfer reactions on metal surfaces. With the assistance of aryl halide precursors, the coupling of terminal alkynes is steered from non-dehydrogenated to dehydrogenated products, resulting in alkynyl-Ag-alkynyl bonds. Dehalogenated molecules are fully passivated by detached hydrogen atoms. The reaction mechanism is unraveled by various surface-sensitive technologies and density functional theory calculations. Moreover, we reveal the universality of this mechanism on metal surfaces. Our studies enrich the on-surface synthesis toolbox and develop a pathway for producing low-dimensional organic materials.

3.
Exp Cell Res ; 435(2): 113932, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38246397

RESUMO

RNA binding protein RBM10 participates in various RNA metabolism, and its decreased expression or loss of function by mutation has been identified in many human cancers. However, how its dysregulation contributes to human cancer pathogenesis remains to be determined. Here, we found that RBM10 expression was decreased in breast tumors, and breast cancer patients with low RBM10 expression presented poorer survival rates. RBM10 depletion in breast cancer cells significantly promotes the cellular proliferation and migration. We further demonstrated that RBM10 forms a triple complex with YBX1 and phosphatase 1B (PPM1B), in which PPM1B serves as the phosphatase of YBX1. RBM10 knock-down markedly attenuated association between YBX1 and PPM1B, leading to elevated levels of YBX1 phosphorylation and its nuclear translocation. Furthermore, cancer cells with RBM10 depletion had a significantly accelerated tumor growth in nude mice. Importantly, these enhanced tumorigenic phenotypes can be reversed by overexpression of PPM1B. Our findings provide the mechanistic bases for functional loss of RBM10 in promoting tumorigenicity, and are potentially useful in the development of combined therapeutic strategies for cancer patients with defective RBM10.


Assuntos
Neoplasias da Mama , Carcinogênese , Animais , Camundongos , Humanos , Feminino , Camundongos Nus , Carcinogênese/genética , Fosforilação , Proliferação de Células/genética , Neoplasias da Mama/genética , Neoplasias da Mama/metabolismo , Monoéster Fosfórico Hidrolases/genética , Regulação Neoplásica da Expressão Gênica , Linhagem Celular Tumoral , Proteína 1 de Ligação a Y-Box/genética , Proteína 1 de Ligação a Y-Box/metabolismo , Proteínas de Ligação a RNA/metabolismo , Proteína Fosfatase 2C/genética , Proteína Fosfatase 2C/metabolismo
4.
Front Optoelectron ; 16(1): 37, 2023 Nov 17.
Artigo em Inglês | MEDLINE | ID: mdl-37975944

RESUMO

Although perovskite light-emitting diodes (PeLEDs) have seen unprecedented development in device efficiency over the past decade, they suffer significantly from poor operational stability. This is especially true for blue PeLEDs, whose operational lifetime remains orders of magnitude behind their green and red counterparts. Here, we systematically investigate this efficiency-stability discrepancy in a series of green- to blue-emitting PeLEDs based on mixed Br/Cl-perovskites. We find that chloride incorporation, while having only a limited impact on efficiency, detrimentally affects device stability even in small amounts. Device lifetime drops exponentially with increasing Cl-content, accompanied by an increased rate of change in electrical properties during operation. We ascribe this phenomenon to an increased mobility of halogen ions in the mixed-halide lattice due to an increased chemically and structurally disordered landscape with reduced migration barriers. Our results indicate that the stability enhancement for PeLEDs might require different strategies from those used for improving efficiency.

5.
J Anim Sci ; 1012023 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-37455295

RESUMO

Water buffalo milk is a reliable source of high-quality nutrients; however, the susceptibility of mastitis in buffaloes must be taken into consideration. An animal with somatic cell count (SCC) of greater than 250,000 cells/mL is reported to be likely to have mastitis which has serious adverse effects on animal health, reproduction, milk yield, and milk quality. Type traits (TTs) of water buffalo can affect SCC in animal milk to some extent, but few reports on the correlation between SCC and TTs are available. In this study, a total of 1908 records collected from 678 water buffaloes were investigated. The general linear model was used to identify factors associated with phenotypic variation of the somatic cell score (SCS) trait, including parity, lactation length, calving year, and calving season as fixed effects. Using PROC CORR analysis method, taking calving year and lactation length as covariates, the correlation co-efficient between TT and SCS was obtained. Our results showed that correlation co-efficients between the 45 TTs with SCS ranged from 0.003 to 0.443 (degree of correlation). The correlation between udder traits and SCS was greater than that between body structure traits and SCS. Among udder traits, distance between teats (including front and rear teat distance [r = 0.308], front teat distance [r = 0.211], and teat crossing distance [r = 0.412]) and teat circumference (r = 0.443) had the highest correlation with SCS, followed by the leg traits including rear leg height (r = -0.354) and hock bend angle (r = -0.170). Animal with high rear legs (>48 cm) and short teat crossing distance (<17 cm), and narrow teat circumference (<11 cm) exhibited low SCS. Using four nonlinear models (Von Bertalanffy, Brody, Logistic, and Gompertz), the optimal growth curves of the TTs highly correlated with the SCS (rear leg height and teat crossing distance) were fitted, and the correction co-efficients of these two TTs rear leg height and teat crossing distance of animal from young age (2 mo old) to first lactation (35 mo old) were attained for establishment of early selection method for water buffaloes with low SCS. This study provides theoretical support for early selection of low-SCS water buffaloes and lays a foundation for improving milk quality and promoting healthy development of water buffalo's dairy industry.


Some type traits (TTs) have been reported to affect somatic cell count (SCC) in bovine milk, which result in mastitis to some extent, but the correlation between SCC and TTs of water buffalo has been poorly understood. Here, a total of 1908 records from 678 buffaloes were investigated. The correlation between 45 TTs and somatic cell score (SCS) was analysed, and the optimal growth curves of TTs highly correlated with SCS were fitted. Our result showed that high rear legs (>48 cm) and short teat crossing distance (<17 cm), and narrow teat circumference (<11 cm) were correlated with low SCS. We obtained correction co-efficients for two TTs highly correlated with SCS of water buffalos from young age (2 mo old) to first lactation (35 mo) by fitting the optimal growth curve for rear leg height and teat crossing distance. This study provides theoretical support for early selection for water buffaloes that are less susceptible to mastitis, and lays a foundation for improving milk quality and promoting healthy development of water buffalo dairy industry.


Assuntos
Búfalos , Mastite , Gravidez , Feminino , Animais , Glândulas Mamárias Animais , Leite/metabolismo , Lactação , Contagem de Células/veterinária , Mastite/metabolismo , Mastite/veterinária
6.
Angew Chem Int Ed Engl ; 62(19): e202218211, 2023 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-36857418

RESUMO

Bicyclo[1.1.1]pentane (BCP) motifs are of growing importance to the pharmaceutical industry as sp3 -rich bioisosteres of benzene rings and as molecular building blocks in materials science. Herein we explore the behavior of 1,3-disubstituted BCP moieties on metal surfaces by combining low-temperature scanning tunneling microscopy / non-contact atomic force microscopy studies with density functional theory modeling. We examine the configuration of individual BCP-containing precursors on Au(111), their supramolecular assembly and thermally activated dehalogenative coupling reactions, affording polymeric chains with incorporated electronically isolating units. Our studies not only provide the first sub-molecular insights of the BCP scaffold behavior on surfaces, but also extend the potential application of BCP derivatives towards integration in custom-designed surface architectures.

7.
Foods ; 12(6)2023 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-36981127

RESUMO

Buffalo milk is a dairy product that is considered to have a higher nutritional value compared to cow's milk. Linoleic acid (LA) is an essential fatty acid that is important for human health. This study aimed to investigate and validate the use of Fourier transform mid-infrared spectroscopy (FT-MIR) for the quantification of the linoleic acid in buffalo milk. Three machine learning models were used to predict linoleic acid content, and random forest was employed to select the most important subset of spectra for improved model performance. The validity of the FT-MIR methods was evaluated in accordance with ICH Q2 (R1) guidelines using the accuracy profile method, and the precision, the accuracy, and the limit of quantification were determined. The results showed that Fourier transform infrared spectroscopy is a suitable technique for the analysis of linoleic acid, with a lower limit of quantification of 0.15 mg/mL milk. Our results showed that FT-MIR spectroscopy is a viable method for LA concentration analysis.

8.
Foods ; 12(6)2023 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-36981245

RESUMO

Colostrum is a vital performance for buffaloes and potentially functional foods in the future. Therefore, this study aimed to evaluate the difference between the parity of buffalo colostrum and mature milk. Twenty pregnant buffaloes (primiparous = 10; multiparous = 10) were assigned to the same diet prepartum and milking routine postpartum. Calves were separated from the dams immediately after birth and colostrum was harvested within 2 h, whilst mature milk was harvested at 7 days postpartum. The colostrum was analyzed for immunoglobulin G and milk composition as the mature milk. The results showed that there was a higher level of protein, solid not fat, and milk urea nitrogen (p < 0.05), with a tendency for higher total solids (p = 0.08) in primiparous buffaloes' colostrum compared with multiparous. No parity effect was observed in colostrum immunoglobulin G, fat, lactose, and yields of colostrum and composition (p > 0.05). There was no difference in mature milk composition and yield by parity affected (p > 0.05). Compared with mature milk composition, colostrum had a higher content protein, total solids, solid not fat, and milk urea nitrogen (p < 0.05); however, fat and lactose were lower than that of mature milk (p < 0.05). For minerals, multiparous buffaloes' colostrum had a higher concentration of Fe (p = 0.05), while the mature milk had higher concentrations of K and P compared with primiparous. Buffalo colostrum had higher concentrations of Na, Mg, Co, Fe, and K with a lower concentration of Ca relative to mature milk (p < 0.05). It was observed that parity affected colostrum characteristics rather than mature milk and caused subtle variations in minerals in colostrum and mature milk of buffaloes. As lactation proceeded, both milk composition and minerals in the milk changed drastically.

9.
Front Endocrinol (Lausanne) ; 14: 1076404, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36891049

RESUMO

Introduction: Inhibin DNA vaccine has already been proven to improve the fertility of animals. This study aimed to investigate the effects of a novel Anti-Müllerian hormone (AMH)-Inhibin (INH)-RF-amide-related peptides (RFRP) DNA vaccine on immune response and reproductive performance in buffalo. Methods: A total of 84 buffaloes were randomly divided into four groups and nasally immunized twice a day with 10 ml of either AMH-INH-RFRP DNA vaccines (3 × 1010 CFU/ml in group T1, 3 × 109 CFU/ml in group T2, and 3 × 108 CFU/ml in group T3) or PBS (as a control) for 3 days, respectively. All animals received a booster dose at an interval of 14 days. Results: ELISA assay revealed that primary and booster immunization significantly increased the anti-AMH, anti-INH, and anti-RFRP antibody titers in the T2 group compared with that in the T3 group. After the primary immunization, the antibody positive rate was significantly higher in the T2 group than that in the T3 group. In addition, ELISA results indicated that concentrations of E2, IFN-γ, and IL-4 were significantly higher in the antibody-positive (P) group compared to the antibody-negative (N) group. In contrast, there was no significant difference in the concentrations of P4 between the P and N groups. Ultrasonography results revealed a highly significant increase of 2.02 mm in the diameter of ovulatory follicles in the P group compared to the N group. In parallel, growth speed of dominant follicles was significantly higher in the P group than that in the N group (1.33 ± 1.30 vs 1.13 ± 0.12). Furthermore, compared to N group, the rates of oestrus, ovulation, and conception were also significantly higher in the P group. Conclusion: The novel AMH-INH-RFRP DNA vaccine improves the proportion of oestrus, ovulation, and conception in buffalo by promoting the production of E2 and the growth of follicles.


Assuntos
Inibinas , Vacinas de DNA , Feminino , Animais , Búfalos/fisiologia , Hormônio Antimülleriano , Fertilidade , Imunização
10.
Animals (Basel) ; 13(5)2023 Feb 25.
Artigo em Inglês | MEDLINE | ID: mdl-36899699

RESUMO

Different bedding materials have important effects on the behavioristics, production performance and welfare of buffalo. This study aimed to compare the effects of two bedding materials on lying behavior, production performance and animal welfare of dairy buffaloes. More than 40 multiparous lactating buffaloes were randomly divided into two groups, which were raised on fermented manure bedding (FMB) and chaff bedding (CB). The results showed that the application of FMB improved the lying behavior of buffaloes, the average daily lying time (ADLT) of buffaloes in FMB increased by 58 min compared to those in CB, with a significant difference (p < 0.05); the average daily standing time (ADST) decreased by 30 min, with a significant difference (p < 0.05); and the buffalo comfort index (BCI) increased, but the difference was not significant (p > 0.05). The average daily milk yield of buffaloes in FMB increased by 5.78% compared to buffaloes in CB. The application of FMB improved the hygiene of buffaloes. The locomotion score and hock lesion score were not significantly different between the two groups and all buffaloes did not show moderate and severe lameness. The price of FMB was calculated to be 46% of CB, which greatly reduced the cost of bedding material. In summary, FMB has significantly improved the lying behavior, production performance and welfare of buffaloes and significantly reduce the cost of bedding material.

11.
Int J Mol Sci ; 24(3)2023 Jan 26.
Artigo em Inglês | MEDLINE | ID: mdl-36768756

RESUMO

Understanding the genetic mechanisms underlying milk production traits contribute to improving the production potential of dairy animals. Squalene epoxidase (SQLE) is one of the rate-limiting enzymes for cholesterol biosynthesis and was highly expressed in the buffalo mammary. The objectives of the present study were to detect the polymorphisms within SQLE in buffalo, the genetic effects of these mutations on milk production traits, and to understand the gene regulatory effects on buffalo mammary epithelial cells (BuMECs). A total of five SNPs were identified by sequencing, g.18858G > A loci were significantly associated with fat yield, and g.22834C > T loci were significantly associated with peak milk yield, milk yield, fat yield, and protein yield. Notably, linkage disequilibrium analysis indicated that 2 SNPs (g.18858G > A and g.22834C > T) formed one haplotype block, which was found to be significantly associated with milk fat yield, fat percentage, and protein yield. Furthermore, expression of SQLE was measured in different tissues of buffalo and was found to be higher in the mammary. Knockdown of SQLE gene expression significantly affected the growth of BuMECs, including proliferation, cell cycle, and apoptosis, and significantly downregulated the expression of related genes MYC, PCNA, and P21. In addition, knockdown of the SQLE gene significantly reduces triglyceride concentrations and the signal intensity of oil red O staining. In addition, silencing of SQLE was also found to regulate the synthesis and secretion of ß-casein and κ-casein negatively. Furthermore, SQLE knockdown is accompanied by the downregulation of critical genes (RPS6KB1, JAK2, eIF4E, and SREBP1) related to milk fat and protein synthesis. The current study showed the potential of the SQLE gene as a candidate for buffalo milk production traits. It provides a new understanding of the physiological mechanisms underlying buffalo milk production regulation.


Assuntos
Leite , Esqualeno Mono-Oxigenase , Animais , Leite/metabolismo , Esqualeno Mono-Oxigenase/genética , Esqualeno Mono-Oxigenase/metabolismo , Fenótipo , Haplótipos , Polimorfismo de Nucleotídeo Único , Búfalos/genética
12.
J Am Chem Soc ; 145(8): 4545-4552, 2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36794794

RESUMO

On-surface acetylenic homocoupling has been proposed to construct carbon nanostructures featuring sp hybridization. However, the efficiency of linear acetylenic coupling is far from satisfactory, often resulting in undesired enyne products or cyclotrimerization products due to the lack of strategies to enhance chemical selectivity. Herein, we inspect the acetylenic homocoupling reaction of polarized terminal alkynes (TAs) on Au(111) with bond-resolved scanning probe microscopy. The replacement of benzene with pyridine moieties significantly prohibits the cyclotrimerization pathway and facilitates the linear coupling to produce well-aligned N-doped graphdiyne nanowires. Combined with density functional theory calculations, we reveal that the pyridinic nitrogen modification substantially differentiates the coupling motifs at the initial C-C coupling stage (head-to-head vs head-to-tail), which is decisive for the preference of linear coupling over cyclotrimerization.

13.
Nanoscale Horiz ; 8(3): 368-376, 2023 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-36629866

RESUMO

We have computationally studied the formation mechanism of the biphenylene network via the intermolecular HF zipping, as well as identified key intermediates experimentally, on the Au(111) surface. We elucidate that the zipping process consists of a series of defluorinations, dehydrogenations, and C-C coupling reactions. The Au substrate not only serves as the active site for defluorination and dehydrogenation, but also forms C-Au bonds that stabilize the defluorinated and dehydrogenated phenylene radicals, leading to "standing" benzyne groups. Despite that the C-C coupling between the "standing" benzyne groups is identified as the rate-limiting step, the limiting barrier can be reduced by the adjacent chemisorbed benzyne groups. The theoretically proposed mechanism is further supported by scanning tunneling microscopy experiments, in which the key intermediate state containing chemisorbed benzyne groups can be observed. This study provides a comprehensive understanding towards the on-surface intermolecular HF zipping, anticipated to be instructive for its future applications.

14.
J Am Chem Soc ; 144(47): 21596-21605, 2022 11 30.
Artigo em Inglês | MEDLINE | ID: mdl-36383110

RESUMO

On-surface synthesis is a powerful methodology for the fabrication of low-dimensional functional materials. The precursor molecules usually anchor on different metal surfaces via similar configurations. The activation energies are therefore solely determined by the chemical activity of the respective metal surfaces. Here, we studied the influence of the detailed adsorption configuration on the activation energy on different metal surfaces. We systematically studied the desulfonylation homocoupling for a molecular precursor on Au(111) and Ag(111) and found that the activation energy is lower on inert Au(111) than on Ag(111). Combining scanning tunneling microscopy observations, synchrotron radiation photoemission spectroscopy measurements, and density functional theory calculations, we elucidate that the phenomenon arises from different molecule-substrate interactions. The molecular precursors anchor on Au(111) via Au-S interactions, which lead to weakening of the phenyl-S bonds. On the other hand, the molecular precursors anchor on Ag(111) via Ag-O interactions, resulting in the lifting of the S atoms. As a consequence, the activation barrier of the desulfonylation reactions is higher on Ag(111), although silver is generally more chemically active than gold. Our study not only reports a new type of on-surface chemical reaction but also clarifies the influence of detailed adsorption configurations on specific on-surface chemical reactions.


Assuntos
Ouro , Prata , Ouro/química , Prata/química , Conformação Molecular , Adsorção
15.
Animals (Basel) ; 12(22)2022 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-36428299

RESUMO

This study aimed to evaluate the efficacy and safety of the SS DNA vaccine on growing pigs. Randomly, 147 pigs were divided into four groups, treatment 1 (T1, 3 × 109 CFU/mL, n = 39), T2 (3 × 108 CFU/mL, n = 35), T3 (3 × 107 CFU/mL, n = 35) and control group (phosphate-buffered saline, n = 38). All animals received two vaccinations separated by 45 days and the same diet and management. The results showed that all treatment groups (T1, T2 and T3) had significantly higher slaughter weight (d 185) than the Ctrl group (p < 0.05), and daily gain between 50 and 110 days of age was significantly higher in all treatment groups than in the Ctrl group (p < 0.05). Antibody-positive pigs have significantly higher daily weight gain than that in antibody-negative pigs (p < 0.05). The results of the meat quality analysis showed no significant changes between the P (antibody-positive pigs) and N (antibody-negative pigs) groups. Furthermore, the results showed that antibody titres at 110 and 185 days had a significant positive correlation with the daily weight gain (p < 0.05) and a significant negative correlation with the backfat thickness (p < 0.05). Evaluating the safety of vaccines by PCR amplification of target genes (GS/2SS), faecal, soil and water samples had no target genes detected by PCR amplification in these samples after 5 days, and no GS/2SS were detected in the blood and tissues for the experimental period. Moreover, no abnormalities were found in pathological sections of the P group compared with the N group. In conclusion, SS DNA vaccines can promote the growth of fattening pigs to a certain extent without altering the meat quality, and it has no effects on the safety of the surrounding environment.

16.
Animal ; 16(11): 100653, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36228548

RESUMO

Type traits (TTs) can contribute to breeding animals with good economic traits such as production, longevity, fertility, and profitability. Dairy buffaloes are the second largest source of milk supply in the world, and their TTs should be taken into consideration in future dairy buffalo breeding programmes. However, the relationship between TTs and milk production traits in buffalo remains largely unknown. The study aimed to establish an early selection method for buffaloes with desirable milk performance by TTs. Using 1 908 records from 678 buffaloes, the relationship between TTs and milk production traits was analysed and the optimal growth curves of TTs related to milk production traits were constructed. We examined the correlations between 45 TTs (33 body structural, 12 udder and teat morphological traits) and three milk production traits (milk yield (MY), milk fat percentage (MF), and milk protein percentage (MP)). The results showed that the highest correlation was found between MY and udder circumference (r = 0.438), teat length (r = -0.380) or heart girth (r = -0.341). The teat distance and teat circumference exhibited a significant negative correlation with MF and MP. Rump length was the only trait that had a significant positive correlation with milk production traits, suggesting that milk performance could be comprehensively improved by including rump length in the selection procedure. Notably, we found that high milk production traits was obtained from the buffaloes with short teats (<6 cm), small heart girth (<200 cm), large udder circumference (>104 cm), long rump (>39 cm), and small distance between teats. Moreover, an early selection method for buffaloes with excellent milk performance was developed based on the non-linear models. Brody model exhibited the best fitting effect for heart girth and rump length, while the Logistic model displayed the best fitting effect for teat length. Our findings provide theoretical basis for the early selection of buffaloes with desirable milk performance.


Assuntos
Búfalos , Lactação , Feminino , Animais , Búfalos/genética , Leite/metabolismo , Glândulas Mamárias Animais/anatomia & histologia , Proteínas do Leite/análise
17.
J Phys Chem Lett ; 13(38): 8902-8907, 2022 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-36126251

RESUMO

Self-assembly of identical organometallic supramolecules into ordered superstructures is of great interest in both chemical science and nanotechnology due to its potential to generate neoteric properties through collective effects. In this work, we demonstrate that large-scale self-organization of atomically precise organometallic supramolecules can be achieved through cascaded on-surface chemical reactions, by the combination of intra- and inter-supramolecular interactions. Supramolecules with defined size and shape are first built through intramolecular reaction and intermolecular metal coordination, followed by the formation of well-ordered two-dimensional arrays with the assistance of Br atoms by -C-H···Br interactions. The mechanism of this process has been investigated from the perspectives of thermodynamics and kinetics.

18.
Animals (Basel) ; 12(10)2022 May 18.
Artigo em Inglês | MEDLINE | ID: mdl-35625146

RESUMO

Exposure to the stress (HS) negatively affects physiology, performance, reproduction and welfare of buffalo. However, the mechanisms by which HS negatively affects rumen bacteria and its associated metabolism in buffalo are not well known yet. This study aimed to gain insight into the adaption of bacteria and the complexity of the metabolome in the rumen of six buffalo during HS using 16S rDNA and gas chromatography metabolomics analyses. HS increased respiratory rate (p < 0.05) and skin temperature (p < 0.01), and it decreased the content of acetic acid (p < 0.05) and butyric acid (p < 0.05) in the rumen. Omics sequencing revealed that the relative abundances of Lachnospirales, Lachnospiraceae, Lachnospiraceae_NK3A20_group and Clostridia_UCG-014 were significantly (p < 0.01) higher under HS than non-heat stress conditions. Several bacteria at different levels, such as Lactobacillales, Streptococcus, Leuconostocaceae and Leissella, were significantly (p < 0.05) more abundant in the rumen of the non-heat stress than HS condition. Thirty-two significantly different metabolites closely related to HS were identified (p < 0.05). Metabolic pathway analysis revealed four key pathways: D-Alanine metabolism; Lysine degradation, Tropane; piperidine and pyridine alkaloid biosynthesis; and Galactose metabolism. In summary, HS may negatively affected rumen fermentation efficiency and changed the composition of rumen community and metabolic function.

19.
Angew Chem Int Ed Engl ; 61(30): e202204123, 2022 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-35474405

RESUMO

We describe the on-surface dehalogenative homocoupling of benzylic bromides, namely bis-bromomethyl- and bis-gem-(dibromomethyl) naphthalene as a potential route to either hydrocarbon dimers or conjugated polymers on Au(111). While bis-gem-(dibromomethyl) naphthalene affords different dimers with naphthocyclobutadiene as the key intermediate, bis-bromomethyl naphthalene furnishes a poly(o-naphthylene vinylidene) as a non-conjugated polymer which undergoes dehydrogenation toward its conjugated derivative poly(o-naphthylene vinylene) upon mild annealing. A combination of scanning tunneling microscopy, non-contact atomic force microscopy and density functional theory calculations provides deep insights into the prevailing mechanisms.

20.
J Am Chem Soc ; 144(18): 8214-8222, 2022 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-35442656

RESUMO

Assembly of semiconducting organic molecules with multiple aryl-metal covalent bonds into stable one- and two-dimensional (1D and 2D) metal-organic frameworks represents a promising route to the integration of single-molecule electronics in terms of structural robustness and charge transport efficiency. Although various metastable organometallic frameworks have been constructed by the extensive use of single aryl-metal bonds, it remains a great challenge to embed multiple aryl-metal bonds into these structures due to inadequate knowledge of harnessing such complex bonding motifs. Here, we demonstrate the substrate-modulated synthesis of 1D and 2D metal-organic hybrids (MOHs) with the organic building blocks (perylene) interlinked solely with multiple aryl-metal bonds via the stepwise thermal dehalogenation of 3,4,9,10-tetrabromo-1,6,7,12-tetrachloroperylene and subsequent metal-organic connection on metal surfaces. More importantly, the conversion from 1D to 2D MOHs is completely impeded on Au(111) but dominant on Ag(111). We comprehensively study the distinct reaction pathways on the two surfaces by visually tracking the structural evolution of the MOHs with high-resolution scanning tunneling and noncontact atomic force microscopy, supported by first-principles density functional theory calculations. The substrate-dependent structural control of the MOHs is attributed to the variation of the M-X (M = Au, Ag; X = C, Cl) bond strength regulated by the nature of the metal species.

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