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1.
J Am Chem Soc ; 146(30): 20594-20603, 2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-38767649

RESUMO

Heterophase nanomaterials have sparked significant research interest in catalysis due to their distinctive properties arising from synergistic effects of different components and the formed phase boundary. However, challenges persist in the controlled synthesis of heterophase intermetallic compounds (IMCs), primarily due to the lattice mismatch of distinct crystal phases and the difficulty in achieving precise control of the phase transitions. Herein, orthorhombic/cubic Ru2Ge3/RuGe IMCs with engineered boundary architecture are synthesized and anchored on the reduced graphene oxide. The Ru2Ge3/RuGe IMCs exhibit excellent hydrogen evolution reaction (HER) performance with a high current density of 1000 mA cm-2 at a low overpotential of 135 mV. The presence of phase boundaries enhances charge transfer and improves the kinetics of water dissociation while optimizing the processes of hydrogen adsorption/desorption, thus boosting the HER performance. Moreover, an anion exchange membrane electrolyzer is constructed using Ru2Ge3/RuGe as the cathode electrocatalyst, which achieves a current density of 1000 mA cm-2 at a low voltage of 1.73 V, and the activity remains virtually undiminished over 500 h.

2.
J Am Chem Soc ; 146(29): 20069-20079, 2024 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-38984787

RESUMO

Electrocatalytic nitrate (NO3-) reduction reaction (NO3RR) holds great potential for the conversion of NO3- contaminants into valuable NH3 in a sustainable method. Unfortunately, the nonequilibrium adsorption of intermediates and sluggish multielectron transfer have detrimental impacts on the electrocatalytic performance of the NO3RR, posing obstacles to its practical application. Herein, we initially screen the adsorption energies of three key intermediates, i.e., *NO3, *NO, and *H2O, along with the d-band centers on 21 types of transition metal (IIIV and IB)-Sb/Bi-based intermetallic compounds (IMCs) as electrocatalysts. The results reveal that hexagonal CoSb IMCs possess the optimal adsorption equilibrium for key intermediates and exhibit outstanding electrocatalytic NO3RR performance with a Faradaic efficiency of 96.3%, a NH3 selectivity of 89.1%, and excellent stability, surpassing the majority of recently reported NO3RR electrocatalysts. Moreover, the integration of CoSb IMCs/C into a novel Zn-NO3- battery results in a high power density of 11.88 mW cm-2.

3.
FASEB J ; 37(5): e22906, 2023 05.
Artigo em Inglês | MEDLINE | ID: mdl-37052859

RESUMO

Pulmonary arterial hypertension (PAH) is a progressive and life-threatening disease characterized by pulmonary vascular remodeling, which may cause right heart failure and even death. Accumulated evidence confirmed that microRNA-26 family play critical roles in cardiovascular disease; however, their function in PAH remains largely unknown. Here, we investigated the expression of miR-26 family in plasma from PAH patients using quantitative RT-PCR, and identified miR-26a-5p as the most downregulated member, which was also decreased in hypoxia-induced pulmonary arterial smooth muscle cell (PASMC) autophagy models and lung tissues of PAH patients. Furthermore, chromatin immunoprecipitation (ChIP) analysis and luciferase reporter assays revealed that hypoxia-inducible factor 1α (HIF-1α) specifically interacted with the promoter of miR-26a-5p and inhibited its expression in PASMCs. Tandem mRFP-GFP-LC3B fluorescence microscopy demonstrated that miR-26a-5p inhibited hypoxia-induced PAMSC autophagy, characterized by reduced formation of autophagosomes and autolysosomes. In addition, results showed that miR-26a-5p overexpression potently inhibited PASMC proliferation and migration, as determined by cell counting kit-8, EdU staining, wound-healing, and transwell assays. Mechanistically, PFKFB3, ULK1, and ULK2 were direct targets of miR-26a-5p, as determined by dual-luciferase reporter gene assays and western blots. Meanwhile, PFKFB3 could further enhance the phosphorylation level of ULK1 and promote autophagy in PASMCs. Moreover, intratracheal administration of adeno-miR-26a-5p markedly alleviated right ventricular hypertrophy and pulmonary vascular remodeling in hypoxia-induced PAH rat models in vivo. Taken together, the HIF-1α/miR-26a-5p/PFKFB3/ULK1/2 axis plays critical roles in the regulation of hypoxia-induced PASMC autophagy and proliferation. MiR-26a-5p may represent as an attractive biomarker for the diagnosis and treatment of PAH.


Assuntos
Hipertensão Pulmonar , MicroRNAs , Hipertensão Arterial Pulmonar , Ratos , Animais , Hipertensão Pulmonar/genética , Hipertensão Pulmonar/metabolismo , Remodelação Vascular/genética , Hipóxia/metabolismo , Hipertensão Arterial Pulmonar/genética , MicroRNAs/genética , MicroRNAs/metabolismo , Artéria Pulmonar/metabolismo , Miócitos de Músculo Liso/metabolismo , Autofagia , Proliferação de Células/genética , Movimento Celular/genética , Proteína Homóloga à Proteína-1 Relacionada à Autofagia/metabolismo
4.
Mol Cell Biochem ; 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38967721

RESUMO

Extracellular vesicles (EVs) produced from MSCs were currently considered as a novel therapeutic agent for skin tissue regeneration and repair. Preconditioning stem cells may activate more molecular pathways and release more bioactive agents. In this study, we obtained EVs from normal (N-EVs) and serum- and glucose-deprived (SGD-EVs) human umbilical cord mesenchymal stem cells (HUCMSCs), and showed that SGD-EVs promoted the migration, proliferation, and tube formation of HUVECs in vitro. In vivo experiments utilizing a rat model show that both N-EVs and SGD-EVs boosted angiogenesis of skin defects and accelerated skin wound healing, while treating wounds with SGD-EVs led to faster skin healing and enhanced angiogenesis. miRNA sequencing showed that miR-29a-3p was abundant in SGD-EVs, and overexpressing miR-29a-3p enhanced the angiogenic ability of HUVECs, while inhibiting miR-29a-3p presented the opposite effect. Further studies demonstrated that miR-29a-3p directly targeted CTNNBIP1, which mediated angiogenesis of HUCMSCs-derived EVs through inhibiting CTNNBIP1 to activate Wnt/ß-catenin signaling pathway. Taken together, these findings suggested that SGD-EVs promote angiogenesis via transferring miR-29a-3p, and activation of Wnt/ß-catenin signaling pathway played a crucial role in SGD-EVs-induced VEGFA production during wound angiogenesis. Our results offered a new avenue for modifying EVs to enhance tissue angiogenesis and augment its role in skin repair.

5.
J Fluoresc ; 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38878194

RESUMO

Nitrite ion is one of the materials widely used in human life, and the accurate, sensitive and stable detection of nitrite ions is of great significance to people's healthy life. In this study, nitrogen-doped fluorescent carbon dots (N-CDs) for detecting nitrite salt solutions were prepared using citric acid monohydrate and Chrysoidin as precursors through a one-pot hydrothermal method. Under the condition of pH = 3, a noticeable quenching phenomenon occurred in the carbon dot solution with the increase in nitrite ion concentration. This quenching effect might be attributed to the diazonium effect. N-CDs have been successfully used as fluorescence probes for NO2- detection. NO2- can effectively quench the fluorescence intensity of N-CDs, providing a linear response to fluorescence quenching efficiency with respect to NO2- concentration within the range of 0-10µM and 10-30µM, and a detection limit of 52nM, showing high sensitivity. In addition, the probe was applied to the determination of NO2- in ham sausage samples with a detection limit of 0.67µM and recoveries in the range of 99.5-102.3%, the fluorescent probe showed satisfactory reliability.

6.
J Fluoresc ; 34(2): 905-913, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37418199

RESUMO

With the expansion of human activities, the consequent influx of mercury (Hg) into the food chain and the environment is seriously threatening human life. Herein, nitrogen and sulfur co-doped fluorescent carbon quantum dots (yCQDs) were prepared via a hydrothermal method using o-phenylenediamine (OPD) and taurine as precursors. The morphological characteristics as well as spectral features of yCQDs indicated that the photoluminescence mechanism should be the molecular state fluorophores of 2, 3-diaminophenothiazine (oxOPD), which is the oxide of OPD. The as-synthesized yCQDs exhibited sensitive recognition of Hg2+. According to the investigation in combination of UV-Vis absorption spectra, time-resolved fluorescence spectra and quantum chemical calculations, the abundant functional groups on the surface of yCQDs allowed Hg2+ to bind with yCQDs through various interactions, and the formed complexes significantly inhibited the absorption of excitation light, resulting in the static fluorescence quenching of yCQDs. The proposed yCQDs was utilized for Hg2+ sensing with the limit of detection calculated to be 4.50 × 10- 8 M. Furthermore, the recognition ability of yCQDs for Hg2+ was estimated in tap water, lake water and bottled water, and the results indicated that yCQDs have potential applications in monitoring Hg2+.

7.
J Fluoresc ; 2024 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-38305987

RESUMO

In this paper, we obtained nitrogen and phosphorus co-doped carbon dots through a hydrothermal method using o-phenylenediamine and citric acid in a 40% phosphoric acid environment. The carbon dots emitted fluorescence at 476 nm under excitation at 408 nm and exhibited good selectivity and high sensitivity towards mercury ions. These carbon dots showed excellent dispersibility in water and maintained stable fluorescence even in high concentration salt environments. The interaction between mercury ions and functional groups on the carbon dots surface through electrostatic interaction resulted in static quenching. Simultaneously, by detecting the lifetime and transient absorption spectra of the carbon dots, we observed that the coordination of mercury ions with the carbon dots broadened the band structure of the carbon dots, and the existing photoinduced electron transfer process increased the non-radiative transition channel. The combined effect of dynamic quenching and static quenching significantly reduced the fluorescence intensity of the carbon dots at 476 nm. The carbon dots exhibited linear detection of mercury ions in the range of 0.01-1 µM, with a detection limit as low as 0.0245 µM. In terms of practical water environmental detection applications, these carbon dots were able to effectively detect mercury ions in tap water and lake water, demonstrating their broad application prospects in the field of environmental metal analysis.

8.
J Fluoresc ; 2024 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-38538960

RESUMO

Herein, we developed a sophisticated dual-mode sensor that utilized 3-aminophenylboric acid functionalized carbon dots (APBA-CDs) to accurately detect uric acid (UA). Our innovative process involved synthesizing APBA-CDs that emitted at 369 nm using a one-step hydrothermal method with 3-aminophenylboric acid and L-glutamine as precursors, ethanol and deionized water as solvents. Once UA was introduced to the APBA-CDs, the fluorescence of the system became visibly quenched. The results of Zeta potential, Fourier transformed infrared (FTIR) spectra, fluorescence lifetime, and other characteristics were analyzed to determine that the reaction mechanism was static quenching. This meant that after UA was mixed with APBA-CDs, it combined with the boric acid function on the surface to form complexes, resulting in a decrease in fluorescence intensity and a blue shift in the absorption peak at about 295 nm in the Ultraviolet-visible (UV-vis) absorption spectra. We were pleased to report that we have successfully used the dual-reading platform to accurately detect UA in serum and human urine. It provided a superior quantitative and visual analysis of UA without the involvement of enzymes. We firmly believe that our innovative dual-mode sensor has immense potential in the fields of biosensing and health monitoring.

9.
J Fluoresc ; 2024 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-38457076

RESUMO

Herein, a fluorescent "on-off-on" nanosensor based on N,S-CDs was developed for highly precise and sensitive recognition of Hg2+ and ampicillin (AMP). Nitrogen and sulfur co-doped carbon dots with blue fluorescence were synthesized by one-pot hydrothermal method using ammonium citrate and DL-methionine as precursors. N,S-CDs exhibited a surface abundant in -OH, -COOH, and -NH2 groups, aiding in creating non-fluorescent ground state complexes when combined with Hg2+, leading to the suppression of N,S-CDs' fluorescence. Subsequent to additional AMP application, the mixed system's fluorescence was restored. Based on this N,S-CDs sensing system, the thresholds for detection for AMP and Hg2+ were discovered to be 0.121 µM and 0.493 µM, respectively. Furthermore, this methodology proved effective in identifying AMP in real samples of tap and lake water, yielding satisfactory results. Consequently, in the area of bioanalysis in intricate environmental sample work, the sensing system showed tremendous promise.

10.
J Nanobiotechnology ; 22(1): 191, 2024 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-38637832

RESUMO

BACKGROUND: Exosomes assume a pivotal role as essential mediators of intercellular communication within tumor microenvironments. Within this context, long noncoding RNAs (LncRNAs) have been observed to be preferentially sorted into exosomes, thus exerting regulatory control over the initiation and progression of cancer through diverse mechanisms. RESULTS: Exosomes were successfully isolated from cholangiocarcinoma (CCA) CTCs organoid and healthy human serum. Notably, the LncRNA titin-antisense RNA1 (TTN-AS1) exhibited a conspicuous up-regulation within CCA CTCs organoid derived exosomes. Furthermore, a significant elevation of TTN-AS1 expression was observed in tumor tissues, as well as in blood and serum exosomes from patients afflicted with CCA. Importantly, this hightened TTN-AS1 expression in serum exosomes of CCA patients manifested a strong correlation with both lymph node metastasis and TNM staging. Remarkably, both CCA CTCs organoid-derived exosomes and CCA cells-derived exosomes featuring pronounced TTN-AS1 expression demonstrated the capability to the proliferation and migratory potential of CCA cells. Validation of these outcomes was conducted in vivo experiments. CONCLUSIONS: In conclusion, our study elucidating that CCA CTCs-derived exosomes possess the capacity to bolster the metastasis tendencies of CCA cells by transporting TTN-AS1. These observations underscore the potential of TTN-AS1 within CTCs-derived exosomes to serve as a promising biomarker for the diagnosis and therapeutic management of CCA.


Assuntos
Colangiocarcinoma , Exossomos , MicroRNAs , Células Neoplásicas Circulantes , RNA Bacteriano , RNA Longo não Codificante , Humanos , MicroRNAs/metabolismo , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , Exossomos/metabolismo , Conectina/genética , Conectina/metabolismo , Linhagem Celular Tumoral , Progressão da Doença , Proliferação de Células , Movimento Celular , Colangiocarcinoma/genética , Colangiocarcinoma/metabolismo , Colangiocarcinoma/patologia , Regulação Neoplásica da Expressão Gênica , Microambiente Tumoral
11.
Mikrochim Acta ; 191(5): 233, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38568427

RESUMO

Nitrogen, boron co-doped carbon quantum dots (gCQDs), and a coloration probe (PPD-NPs) with response to cobalt ions (Co2+) were prepared by using 4-hydroxyphenylboric acid as the common precursor, with ethylenediamine and p-phenylenediamine (PPD) adopted as nitrogen-doped reagents, respectively. A noticeable brown-to-purple color change can be observed with the addition of Co2+, and a broad absorption band emerges at 535 nm. At the same time, gCQDs, which is introduced as the fluorescence signal source, will be significantly quenched due to the enhanced inner filtration effect, induced by the overlap between the emission spectrum of gCQDs and the emerging absorption band. Therefore, a colorimetric/fluorescent dual-mode sensing probe for Co2+ is constructed by combining the recognition unit PPD-NPs and the fluorescent gCQDs into PPD-NP/gCQD. Under the optimized experimental conditions, the calculated limits of detection are 1.51 × 10-7 M and 3.75 × 10-7 M for the colorimetric mode and the fluorescence mode, respectively, well qualified for the determination of Co2+ maximum permitted level in drinking water. The feasibility of the proposed method has been verified in tap water, lake water, and black tea samples.

12.
Mikrochim Acta ; 191(9): 529, 2024 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-39123066

RESUMO

A ratiometric fluorescence probe based on carbon quantum dots with 420 nm emission (bCQDs) and a p-phenylenediamine-derived fluorescence probe with 550 nm emission (yprobe) is constructed for the detection of Mn2+. The presence of Mn2+ results in the enhanced absorption band at 400 nm of yprobe, and the fluorescence of yprobe is significantly enhanced based on the chelation-enhanced fluorescence mechanism. The fluorescence of bCQDs is then quenched based on the inner filtration effect. The ratio (I550/I420) linearly increases with the increase of Mn2+ concentration within 2.00 × 10-7-1.50 × 10-6 M, and the limit of detection is 1.76 × 10-9 M. Given the fluorescence color changing from blue to yellow, the visual sensing of Mn2+ is feasible based on bCQDs/yprobe coupled with RGB value analysis. The practicability of the proposed method has been verified in tap water, lake water, and sparkling water beverage, indicating that bCQDs/yprobe has promising application in Mn2+ monitoring.

13.
BMC Surg ; 24(1): 14, 2024 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-38172778

RESUMO

BACKGROUND: To explore the learning curve of single center laparoscopic pancreaticoduodenectomy (LPD) and evaluate the safety and efficacy of the operation at different stages. METHODS: A detailed review was conducted on the clinical data of 120 cases of laparoscopic pancreatoduodenectomy performed by the same surgeon between June 2018 and June 2022. Cases that did not provide insights into the learning curve of the procedure were excluded. The cumulative sum (CUSUM) analysis and the best fitting curve methods were employed to delineate the learning curve based on operation time and intraoperative blood loss. The study further evaluated the number of surgeries required to traverse the learning curve. Outcome measures, including operation time, intraoperative blood loss, length of stay, complications, and other relevant indicators, were extracted and compared across different phases of the learning curve. RESULT: The maximum turning point of the fitting curve was found in 35 cases by the cumulative sum method of operation time, after which the learning curve could be considered to have passed. The fitting curve obtained by the cumulative sum method of intraoperative blood loss was stable in 30 cases and proficient in 60 cases, which was basically consistent with the fitting curve of operation time. Taking 35 cases as the boundary, the learning curve is divided into learning improvement stage and mastering stage. There was no statistical significance in the general data of the two stage patients (P > 0.05). Hospitalization days decreased from 19 to 15 days (P < 0.05);Pancreatic fistula decreased from 20.0% of grade B and 8.6% of grade C to 7.1% of grade B and 3.5% of grade C (P < 0.05), and the operative time decreased from (376.9 ± 48.2) minutes to (294.4 ± 18.7) minutes (P < 0.05). Intraoperative blood loss decreased from 375 to 241 ml (P < 0.05). CONCLUSION: Thirty-five patients with LPD can reach the proficiency stage and the perioperative indexes can be improved.


Assuntos
Laparoscopia , Cirurgiões , Humanos , Estudos Retrospectivos , Pancreaticoduodenectomia/métodos , Perda Sanguínea Cirúrgica , Curva de Aprendizado , Tempo de Internação , Laparoscopia/métodos , Duração da Cirurgia , Complicações Pós-Operatórias/etiologia
14.
Angew Chem Int Ed Engl ; 63(25): e202405173, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38622784

RESUMO

Constructing amorphous/intermetallic (A/IMC) heterophase structures by breaking the highly ordered IMC phase with disordered amorphous phase is an effective way to improve the electrocatalytic performance of noble metal-based IMC electrocatalysts because of the optimized electronic structure and abundant heterophase boundaries as active sites. In this study, we report the synthesis of ultrathin A/IMC PtPbBi nanosheets (NSs) for boosting hydrogen evolution reaction (HER) and alcohol oxidation reactions. The resulting A/IMC PtPbBi NSs exhibit a remarkably low overpotential of only 25 mV at 10 mA cm-2 for the HER in an acidic electrolyte, together with outstanding stability for 100 h. In addition, the PtPbBi NSs show high mass activities for methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR), which are 13.2 and 14.5 times higher than those of commercial Pt/C, respectively. Density functional theory calculations demonstrate that the synergistic effect of amorphous/intermetallic components and multimetallic composition facilitate the electron transfer from the catalyst to key intermediates, thus improving the catalytic activity of MOR. This work establishes a novel pathway for the synthesis of heterophase two-dimensional nanomaterials with high electrocatalytic performance across a wide range of electrochemical applications.

15.
Angew Chem Int Ed Engl ; : e202409515, 2024 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-39228207

RESUMO

Gallium (Ga) with a low melting point can serve as a unique metallic solvent in the synthesis of intermetallic compounds (IMCs). The negative formation enthalpy of transition metal-Ga IMCs endows them with high catalytic stability. Meanwhile, their tunable crystal structures offer the possibility to tailor the configurations of active sites to meet the requirements for specific catalytic applications. Herein, we present a general method for preparing a range of transition metal-Ga IMCs, including Co-Ga, Ni-Ga, Pt-Ga, Pd-Ga, and Rh-Ga IMCs. The structurally ordered CoGa IMCs with body-centered cubic (bcc) structure are uniformly dispersed on the nitrogen-doped reduced graphene oxide substrate (O-CoGa/NG) and deliver outstanding nitrate reduction reaction (NO3RR) performance, making them excellent catalysts to construct highly efficient rechargeable Zn-NO3- battery. Operando studies and theoretical simulations demonstrate that the electron-rich environments around the Co atoms enhance the adsorption strength of *NO3 intermediate and simultaneously suppress the formation of hydrogen, thus improving the NO3RR activity and selectivity.

16.
BMC Genomics ; 24(1): 430, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37528394

RESUMO

The tumor immune microenvironment (TIME) of colon cancer (CC) has been associated with extensive immune cell infiltration (IMI). Increasing evidence demonstrated that plasma cells (PC) have an extremely important role in advance of antitumor immunity. Nonetheless, there is a lack of comprehensive analyses of PC infiltration in clinical prognosis and immunotherapy in CC. This study systematically addressed the gene expression model and clinical information of CC patients. Clinical samples were obtained from the TCGA (The Cancer Genome Atlas) databases. Gene ontology (GO), Kyoto Encyclopedia of Genes and Genomes (KEGG), GSVA, and the MAlignant Tumors using Expression data (ESTIMATE) algorithm were employed to research the potential mechanism and pathways. Immunophenoscore (IPS) was obtained to evaluate the immunotherapeutic significance of risk score. Half maximal inhibitory concentration (IC50) of chemotherapeutic medicine was predicted by employing the pRRophetic algorithm. A total of 513 CC samples (including 472 tumor samples and 41 normal samples) were collected from the TCGA-GDC database. Significant black modules and 313 candidate genes were considered PC-related genes by accessing WGCNA. Five pivotal genes were established through multiple analyses, which revealed excellent prognostic. The underlying correlation between risk score with tumor mutation burden (TMB) was further explored. In addition, the risk score was obviously correlated with various tumor immune microenvironment (TIME). Also, risk CC samples showed various signaling pathways activity and different pivotal sensitivities to administering chemotherapy. Finally, the biological roles of the CD177 gene were uncovered in CC.


Assuntos
Neoplasias do Colo , Medicina , Humanos , Plasmócitos , Neoplasias do Colo/genética , Neoplasias do Colo/terapia , Imunoterapia , Algoritmos , Prognóstico , Microambiente Tumoral/genética
17.
J Am Chem Soc ; 145(9): 4934-4939, 2023 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-36811995

RESUMO

Iron porphyrin carbenes (IPCs) have been extensively recognized as the reactive intermediates in various iron porphyrin-catalyzed carbene transfer reactions. While donor-acceptor diazo compounds have been frequently used for such transformations, the structures and reactivities of donor-acceptor IPCs are less explored. To date, no crystal structures of donor-acceptor IPC complexes have been reported, and therefore, the involvement of IPC intermediacy for such transformations lacks direct evidence. Here we report the synthesis and NMR characterization of several donor-acceptor IPC complexes from iron porphyrin and corresponding donor-acceptor diazo compounds. The X-ray crystal structure of an IPC complex derived from a morpholine-substituted diazo amide was obtained. The carbene transfer reactivities of those IPCs were tested by the N-H insertion reactions with aniline or morpholine as well as the three-component reaction with aniline and γ,δ-unsaturated α-keto ester based on electrophilic trapping of an ammonium ylide intermediate. Based on these results, IPCs were identified as the real intermediates for iron porphyrin-catalyzed carbene transfer reactions from donor-acceptor diazo compounds.

18.
Small ; : e2307041, 2023 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-38072798

RESUMO

Developing a self-expanding hemostatic sponge with high blood absorption and rapid shape recovery for noncompressible hemorrhage remains a challenge. In this study, a 3D-printed cuttlefish bone elastomeric sponge (CBES) is fabricated, which combined ordered channels and porous structures, presented tunable mechanical strength, and shape memory potentials. The incorporation of cuttlefish bone powder (CBp) plays key roles in concentrating blood components, promoting aggregation of red blood cells and platelets, and activating platelets, which makes CBES show enhanced hemostatic performance compared with commercial gelatin sponges in vivo. Moreover, CBES promotes more histiocytic infiltration and neovascularization in the early stage of degradation than gelatin sponges, which is conducive to the regeneration and repair of injured tissue. To conclude, CBp loaded 3D-printed elastomeric sponges can promote coagulation, present the potential to guide tissue healing, and broaden the hemostatic application of traditional Chinese medicine.

19.
Cell Biol Toxicol ; 39(4): 1531-1547, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-35809138

RESUMO

DDI2 and DDI3 (DDI2/3) are two identical genes in Saccharomyces cerevisiae encoding cyanamide (CY) hydratase. They are not only highly induced by CY, but also by a DNA-damaging agent methyl methanesulfonate (MMS), and the regulatory mechanism is unknown. In this study, we performed a modified genome-wide genetic synthetic array screen and identified Fzf1 as a zinc-finger transcriptional activator required for CY/MMS-induced DDI2/3 expression. Fzf1 binds to a DDI2/3 promoter consensus sequence CS2 in vivo and in vitro, and this interaction was enhanced in response to the CY treatment. Indeed, experimental over production of Fzf1 alone was sufficient to induce DDI2/3 expression; however, CY and MMS treatments did not cause the accumulation or apparent alteration in migration of cellular Fzf1. To test a hypothesis that Fzf1 is activated by covalent modification of CY and MMS, we performed mass spectrometry of CY/MMS-treated Fzf1 and detected a few modified lysine residues. Amino acid substitutions of these residues revealed that Fzf1-K70A completely abolished MMS-induced and reduced CY-induced DDI2/3 expression, indicating that the Fzf1-K70 methylation activates Fzf1. This study collectively reveals a novel regulatory mechanism by which Fzf1 is activated by chemical modifications and in turn induces the expression of its target genes for detoxification.


Assuntos
Saccharomyces cerevisiae , Fatores de Transcrição , Ativação Transcricional/genética , Saccharomyces cerevisiae/genética , Saccharomyces cerevisiae/metabolismo , Fatores de Transcrição/genética , Fatores de Transcrição/metabolismo
20.
Anal Bioanal Chem ; 415(8): 1397-1409, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36639530

RESUMO

In this paper, we proposed an efficient method for mercury(II) and glutathione detection using a fluorescent nanoprobe as a sensor. Carbon dots were synthesized from polyethyleneimine and ammonium citrate via a one-step hydrothermal method. The fluorescence of carbon dots was quenched since electron transfer occurred due to the interaction between mercury(II) and functional groups on the surface of carbon dots. Adding glutathione to the carbon dots-mercury(II) system, the fluorescence was recovered due to the stronger binding ability of glutathione to mercury(II). Based on the above-mentioned principle, this "off-on" fluorescent sensor can easily achieve the detection of mercury(II) and glutathione, which provided limits of detection of 22.45 nM and 61.89 nM, respectively. In this paper, the proposed method has been applied to detect mercury(II) and glutathione in real lake water and serum, respectively, and a logic gate for sensing glutathione was presented. The developed "off-on" fluorescent sensor with high sensitivity and selectivity has shown great potential for mercury(II) and glutathione detection in environmental and biosensing fields.

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