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1.
Proc Natl Acad Sci U S A ; 120(27): e2300493120, 2023 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-37364112

RESUMO

Fast transport of charge carriers in semiconductor photoelectrodes are a major determinant of the solar-to-hydrogen efficiency for photoelectrochemical (PEC) water slitting. While doping metal ions as single atoms/clusters in photoelectrodes has been popularly used to regulate their charge transport, PEC performances are often low due to the limited charge mobility and severe charge recombination. Here, we disperse Ru and P diatomic sites onto hematite (DASs Ru-P:Fe2O3) to construct an efficient photoelectrode inspired by the concept of correlated single-atom engineering. The resultant photoanode shows superior photocurrent densities of 4.55 and 6.5 mA cm-2 at 1.23 and 1.50 VRHE, a low-onset potential of 0.58 VRHE, and a high applied bias photon-to-current conversion efficiency of 1.00% under one sun illumination, which are much better than the pristine Fe2O3. A detailed dynamic analysis reveals that a remarkable synergetic ineraction of the reduced recombination by a low Ru doping concentration with substitution of Fe site as well as the construction of Ru-P bonds in the material increases the carrier separation and fast charge transportation dynamics. A systematic simulation study further proves the superiority of the Ru-P bonds compared to the Ru-O bonds, which allows more long-lived carriers to participate in the water oxidation reaction. This work offers an effective strategy for enhancing charge carrier transportation dynamics by constructing pair sites into semiconductors, which may be extended to other photoelectrodes for solar water splitting.

2.
Anal Chem ; 96(5): 2078-2086, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38259249

RESUMO

A series of optically active helical poly(phenylacetylene)s (PPA-Pro1, PPA-Pro3, PPA-Pro6, PPA-Pro9, and PPA-Pro12) bearing different chain lengths of L-proline oligopeptide in the side chains were obtained by polymerizing the corresponding novel phenylacetylene monomers. The monomer adopted a trans-rich helix structure when the L-proline oligopeptide chain length was longer, according to the optical activities and 2D-NMR analysis. The helical structure could be maintained and significantly influenced the polymers' helical conformation by introducing the L-proline oligopeptide to the pendants. By the way, the morphology of PPA-Pro3 was observed by atomic force microscope (AFM) on highly oriented pyrolytic graphite (HOPG), and the information on the helix direction, pitch, and chain arrangement was obtained. Also, the chiral separation properties of these polymer-based chiral stationary phases (CSPs) were investigated using high-performance liquid chromatography (HPLC). The poly(phenylacetylene)s showed enhanced enantioseparation properties toward various racemates depending on the longer chain length of the L-proline oligopeptide in the pendants and the positive synergy between the helical backbone and helical side chains. Particularly, PPA-Pro9 showed comparable or even superior enantioseparation properties for racemates 2 and 9 to four commercial columns (Daicel Chiralpak or Chiralcel AD, AS, OD, and OT), indicating that these poly(phenylacetylene)-based CSPs have potential practical values. This work presented here provides inspiration for the further development of CSPs based on a new paradigm.

3.
BMC Plant Biol ; 24(1): 106, 2024 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-38342898

RESUMO

BACKGROUND: The genus Libanotis Haller ex Zinn, nom. cons., a contentious member of Apiaceae, encompasses numerous economically and medicinally significant plants, comprising approximately 30 species distributed across Eurasia. Despite many previous taxonomic insights into it, phylogenetic studies of the genus are still lacking. And the establishment of a robust phylogenetic framework remains elusive, impeding advancements and revisions in the taxonomic system for this genus. Plastomes with greater variability in their genetic characteristics hold promise for building a more robust Libanotis phylogeny. RESULTS: During our research, we sequenced, assembled, and annotated complete plastomes for twelve Libanotis species belong to three sections and two closely related taxa. We conducted a comprehensive comparative analysis through totally thirteen Libanotis plastomes for the genus, including an additional plastome that had been published. Our results suggested that Libanotis plastome was highly conserved between different subclades, while the coding regions were more conserved than the non-coding regions, and the IR regions were more conserved than the single copy regions. Nevertheless, eight mutation hotspot regions were identified among plastomes, which can be considered as candidate DNA barcodes for accurate species identification in Libanotis. The phylogenetic analyses generated a robustly framework for Libanotis and revealed that Libanotis was not a monophyletic group and their all three sections were polygenetic. Libanotis schrenkiana was sister to L. sibirica, type species of this genus, but the remainders scattered within Selineae. CONCLUSION: The plastomes of Libanotis exhibited a high degree of conservation and was effective in enhancing the support and resolution of phylogenetic analyses within this genus. Based on evidence from both phylogeny and morphology, we propose the recognition of "Libanotis sensu stricto" and provide taxonomic recommendations for other taxa that previously belonged to Libanotis. In conclusion, our study not only revealed the phylogenetic position and plastid evolution of Libanotis, but also provided new insights into the phylogeny of the family Apiaceae and phylogenetic relationships within the tribe Selineae.


Assuntos
Apiaceae , Filogenia , Evolução Molecular , Plastídeos/genética , Plantas
4.
Small ; : e2400564, 2024 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-38368264

RESUMO

Developing efficient metal-free catalysts to directly synthesize hydrogen peroxide (H2 O2 ) through a 2-electron (2e) oxygen reduction reaction (ORR) is crucial for substituting the traditional energy-intensive anthraquinone process. Here, in-plane topological defects enriched graphene with pentagon-S and pyrrolic-N coordination (SNC) is synthesized via the process of hydrothermal and nitridation. In SNC, pentagon-S and pyrrolic-N originating from thiourea precursor are covalently grafted onto the basal plane of the graphene framework, building unsymmetrical dumbbell-like S─C─N motifs, which effectively modulates atomic and electronic structures of graphene. The SNC catalyst delivers ultrahigh H2 O2 productivity of 8.1, 7.3, and 3.9 mol gcatalyst -1  h-1 in alkaline, neutral, and acidic electrolytes, respectively, together with long-term operational stability in pH-universal electrolytes, outperforming most reported carbon catalysts. Theoretical calculations further unveil that defective S─C─N motifs efficiently optimize the binding strength to OOH* intermediate and substantially diminish the kinetic barrier for reducing O2 to H2 O2 , thereby promoting the intrinsic activity of 2e-ORR.

5.
Phys Chem Chem Phys ; 26(25): 17561-17568, 2024 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-38869486

RESUMO

Chromium(III)-doped zinc gallate (CZGO) is one of the representative persistent luminescent phosphors emitting in the near-infrared (NIR) region. The emission wavelength it covers falls in the tissue-transparent window, making CZGO a promising optical probe for various biomedical applications. The PersL mechanism dictates that such a phenomenon is only profound in large crystals, so the preparation of CZGO with sizes small enough for biological applications while maintaining its luminescence remains a challenging task. Recent attempts to use mesoporous silica nanoparticles (MSN) as a template for growing nanosized CZGO have been successful. MSN is also a well-studied drug carrier, and incorporating CZGO in MSN further expands its potential in imaging-guided therapeutics. Despite the interest, it is unclear of how the addition of MSN would affect the luminescence properties of CZGO. In this work, we observed that forming a CZGO@MSN nanocomposite could enhance the luminescence intensity and extend the PersL lifetime of CZGO. X-ray absorption fine structure (XAFS) analysis was conducted to investigate the local structure of Zn2+, and an interaction between Zn2+ in CZGO and the MSN matrix was identified.

6.
Angew Chem Int Ed Engl ; 63(14): e202319153, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38356309

RESUMO

As a sustainable valorization route, electrochemical glycerol oxidation reaction (GOR) involves in formation of key OH* and selective adsorption/cleavage of C-C(O) intermediates with multi-step electron transfer, thus suffering from high potential and poor formate selectivity for most non-noble-metal-based electrocatalysts. So, it remains challenging to understand the structure-property relationship as well as construct synergistic sites to realize high-activity and high-selectivity GOR. Herein, we successfully achieve dual-high performance with low potentials and superior formate selectivity for GOR by forming synergistic Lewis and Brønsted acid sites in Ni-alloyed Co-based spinel. The optimized NiCo oxide solid-acid electrocatalyst exhibits low reaction potential (1.219 V@10 mA/cm2) and high formate selectivity (94.0 %) toward GOR. In situ electrochemical impedance spectroscopy and pH-dependence measurements show that the Lewis acid centers could accelerate OH* production, while the Brønsted acid centers are proved to facilitate high-selectivity formation of formate. Theoretical calculations reveal that NiCo alloyed oxide shows appropriate d-band center, thus balancing adsorption/desorption of C-O intermediates. This study provides new insights into rationally designing solid-acid electrocatalysts for biomass electro-upcycling.

7.
Analyst ; 148(8): 1877-1886, 2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-36960700

RESUMO

A novel one-handed helical copoly(phenylacetylene) (CPA) bearing L-proline tripeptide pendants and a few triethoxysilyl residues was synthesized and hybridized into SiO2 porous microspheres (PMSs) during microsphere growth through the hydrolytic polycondensation of ethoxysilyl groups. Nuclear magnetic resonance and Fourier transform infrared spectroscopy results verified the successful preparation of CPA and its hybrid product using SiO2 PMSs. The chiral recognition ability of the resulting CPA with a hybridized-type chiral stationary phase (HCSP) for high-performance liquid chromatography (HPLC) was investigated, revealing its high recognition ability for selected racemates. Moreover, the HCSP showed good solvent tolerability, thus broadening the selection of suitable eluents. The separation effect of the HCSP for the racemate N,N-diphenylcyclohexane-1,2-dicarboxamide (7) improved significantly after introducing CHCl3 in the eluent, resulting in separation factors equivalent or superior to common commercially available polysaccharide-based chiral stationary phases. The proposed preparation strategy provides a new and valuable method for obtaining poly(phenylacetylene)-based HCSPs suitable for a wide range of applications and eluent conditions.

8.
Inorg Chem ; 62(32): 13011-13020, 2023 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-37535952

RESUMO

The field of designing artificial metalloproteins has yet to effectively tackle the incorporation of multimetal clusters, which is a key component of natural metalloproteins, such as metallothioneins (MTs) and calmodulin. MT is a physiological, essential, cysteine-rich metalloprotein that binds to a variety of metals but is only known to form metal-thiolate clusters with Cd2+, Zn2+, and Cu+. Bismuth is a xenobiotic metal and a component of metallodrugs used to treat gastric ulcers and cancer, as well as an emerging metal used in industrial practices. Electrospray ionization mass spectrometry, UV-visible spectroscopy, and extended X-ray absorption fine structure spectroscopy were used to probe the Bi3+ binding site structures in apo-MT3 (brain-located MT) at pH 7.4 and 2 and provide the complete set of binding affinities. We discovered the highly cooperative formation of a novel Bi3+ species, Bi2MT3, under physiological conditions, where each Bi3+ ion is coordinated by three cysteinyl thiolates, with one of the thiolates bridging between the two Bi3+ ions. This cluster structure was associated with a strong visible region absorption band, which was disrupted by the addition of Zn2+ and reversibly disrupted by acidification and increased temperature. This is the first reported presence of bridging cysteines for a xenobiotic metal in MT3 and the Bi2MT structure is the first Bi cluster found in a metalloprotein.

9.
Mol Biol Rep ; 50(3): 2847-2856, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36609753

RESUMO

Recently, researches have revealed the key roles of the cytoskeleton in the occurrence and development of multiple diseases, suggesting that targeting the cytoskeleton is a viable approach for treating numerous refractory diseases. The cytoskeleton is a highly structured and complex network composed of actin filaments, microtubules, and intermediate filaments. In normal cells, these three cytoskeleton components are highly integrated and coordinated. However, the cytoskeleton undergoes drastic remodeling in cytoskeleton-related diseases, causing changes in cell polarity, affecting the cell cycle, leading to senescent diseases, and influencing cell migration to accelerate cancer metastasis. Additionally, mutations or abnormalities in cytoskeletal proteins and their related proteins are closely associated with several congenital diseases. Therefore, this review summarizes the roles of the cytoskeleton in cytoskeleton-related diseases as well as its potential roles in disease treatment to provide insights regarding the physiological functions and pathological roles of the cytoskeleton.


Assuntos
Citoesqueleto , Microtúbulos , Humanos , Citoesqueleto/metabolismo , Microtúbulos/metabolismo , Citoesqueleto de Actina/metabolismo , Filamentos Intermediários/metabolismo , Movimento Celular/fisiologia , Actinas/metabolismo
10.
Environ Res ; 231(Pt 2): 116160, 2023 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-37209988

RESUMO

Practical adsorbents with high efficiency are essential to effectively treating wastewater. Herein, a novel porous uranium adsorbent (PA-HCP) having a considerable amount of amine and phosphoryl groups was designed and synthesized by grafting polyethyleneimine (PEI) on a hyper-cross-linked fluorene-9-bisphenol skeleton via phosphoramidate linkers. Furthermore, it was used to treat uranium contamination in the environment. PA-HCP exhibited a large specific surface area (up to 124 m2/g) and a pore diameter of 2.5 nm. Batch uranium adsorptions on PA-HCP were investigated methodically. PA-HCP demonstrated a uranium sorption capacity of >300 mg/g in the pH range of 4-10 (C0 = 60 mg/L, T = 298.15 K), with its maximum capacity reaching 573.51 mg/g at pH = 7. The uranium sorption process obeyed the pseudo-second-order model and fitted well with the Langmuir isothermal. In the thermodynamic experiments, uranium sorption on PA-HCP was revealed to be an endothermic, spontaneous process. Even in the presence of competing metal ions, PA-HCP exhibited excellent sorption selectivity for uranium. Additionally, excellent recyclability can be achieved after six cycles. Based on FT-IR and XPS measurements, both the PO and -NH2 (and/or -NH-) groups on PA-HCP contributed to efficient uranium adsorption as a result of the strong coordination between these groups and uranium. Furthermore, the high hydrophilicity of the grafted PEI improved the dispersion of the adsorbents in water and facilitated uranium sorption. These findings suggest that PA-HCP can be used as an efficient and economical sorbent to remove U(VI) from wastewater.


Assuntos
Polímeros , Urânio , Água , Águas Residuárias , Polietilenoimina , Espectroscopia de Infravermelho com Transformada de Fourier , Adsorção , Cinética , Concentração de Íons de Hidrogênio
11.
Angew Chem Int Ed Engl ; 62(46): e202306896, 2023 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-37747767

RESUMO

Developing efficient and robust hydrogen evolution reaction (HER) catalysts for scalable and sustainable hydrogen production through electrochemical water splitting is strategic and challenging. Herein, heterogeneous Mo8 O26 -NbNx Oy supported on N-doped graphene (defined as Mo8 O26 -NbNx Oy /NG) is synthesized by controllable hydrothermal reaction and nitridation process. The O-exposed Mo8 O26 clusters covalently confined on NbNx Oy nanodomains provide a distinctive interface configuration and appropriate electronic structure, where fully exposed multiple active sites give excellent HER performance beyond commercial Pt/C catalyst in pH-universal electrolytes. Theoretical studies reveal that the Mo8 O26 -NbNx Oy interface with electronic reconstruction affords near-optimal hydrogen adsorption energy and enhanced initial H2 O adsorption. Furthermore, the terminal O atoms in Mo8 O26 clusters cooperate with Nb atoms to promote the initial H2 O adsorption, and subsequently reduce the H2 O dissociation energy, accelerating the entire HER kinetics.

12.
Phys Chem Chem Phys ; 24(35): 21131-21140, 2022 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-36039710

RESUMO

Near-infrared (NIR)-emitting persistent luminescence (PersL) nanoparticles have attracted great attention as a novel optical probe for bioimaging and biosensing applications. These nanoparticles emit long-lasting luminescence after the removal of the excitation source, which effectively eliminates the interference from tissue autofluorescence. Cr-doped zinc gallate (ZnGa2O4:Cr3+, CZGO) is a representative NIR-emitting PersL material. On the other hand, amorphous calcium phosphate (ACP) is a widely used drug carrier due to its high biocompatibility. In this work, we present a design of an ACP-based drug carrier with PersL properties, by forming a CZGO-ACP composite. The PersL properties of CZGO were preserved by composite formation, while it is found that the Zn2+ could migrate from CZGO to ACP during composite formation, leading to different luminescence mechanisms between pure CZGO and the CZGO-ACP composite. The electronic structure of the composite was analyzed by synchrotron X-ray absorption spectroscopy, and a structure-luminescence correlation was proposed.


Assuntos
Luminescência , Nanopartículas , Cálcio , Portadores de Fármacos , Nanopartículas/química , Fosfatos , Zinco , Compostos de Zinco
13.
Phys Chem Chem Phys ; 24(47): 29034-29042, 2022 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-36427044

RESUMO

Gold nanoclusters (AuNCs) are a unique class of materials that exhibit visible luminescence. Amorphous calcium phosphate (ACP) is a widely used biomaterial for a variety of purposes, such as drug delivery, bone cementing, and implant coatings. In this study, a nanocomposite of AuNCs and ACP is prepared by biomimetic mineralization in a Dulbecco's modified Eagle's medium (DMEM). The strong interaction between AuNCs and Ca2+ ions effectively induces aggregation of AuNCs. The as-formed nanocomposite, AuNCs@ACP, emits significantly enhanced luminescence compared to AuNCs alone. The luminescence enhancement mechanism is investigated using synchrotron X-ray absorption fine structure spectroscopy. In addition, the presence of AuNCs stabilizes ACP and also enhances the biocompatibility of ACP in promoting cell proliferation, and the nanocomposites are promising as nanoprobes for cancer therapy and/or bone tissue engineering.


Assuntos
Biomimética , Ouro , Fosfatos de Cálcio
14.
Chirality ; 34(3): 450-461, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-34997650

RESUMO

For general optical resolution, an optical resolution agent is necessary, and the best agent should be selected for each racemic compound. In this study, we will report that a novel optical resolution method by circularly polarized light (CPL) without any optical resolution agents has been developed by serially connecting two enantioselective reactions. These reactions we developed are the enantiomer-selective helix-sense-selective polymerization (ES-HSSP) and helix-sense-selective highly selective photocyclic aromatization (SCAT) by CPL (HS-SCAT). Since this significantly unique EPHS method (EPHS = ES-HSSP + HS-SCAT) does not need any optical resolution agents, any cocatalysts, and solvents for the selective decomposition reaction (HS-SCAT), this process is quite simple and convenient. Since this process does not include any decomposition of the target racemates themselves, both enantiomers could be obtained. The optical yields for isolated compounds that were enantiomerically separated by the EPHS method were very high, for example, 78%ee, 93%ee, and 85%ee for menthol, phenethyl alcohol, and 2-butanol, respectively. In addition, their chemical yields were around 85% to 94%. Therefore, the EPHS method was found to show an excellent performance and can be applied to actual optical resolution for a wide range of racemic compounds. This is the first absolute optical resolution by CPL showing high optical and chemical yields and expected to become a practical optical resolution method.


Assuntos
Acetileno , Estereoisomerismo
15.
Chirality ; 34(1): 147-159, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34749430

RESUMO

Chiral resolution of binaphthylamine is often a toilful conundrum in the field of analytical chemistry and biomedicine. The work puts forward a selective, sensitive, and miniaturized analytical method based on molecularly imprinted polymers (MIPs) as adsorbent for miniaturized tip solid-phase extraction (MTSPE) in the separation of binaphthylamine enantiomer. This method combines the advantages of MIPs (high selectivity), MTSPE (low consumption), and high-performance liquid chromatography (HPLC, high sensitivity). A simple synthesis methodology of MIP (P2) was conducted through bulk polymerization with (S)-(-)-1,1'-binaphthyl-2,2'-diamine (S-DABN) as template together with methacrylic acid monomer, and ethylene glycol dimethacrylate as cross-linker in proper porogen, realizing a selective recognition and efficient enrichment for S-DABN. The method exhibited appreciable linearity (0.06-1.00 mg ml-1 ), low quantification limit (0.056 mg ml-1 ), good absolute recoveries (45.70%-69.29%), and high precision (relative standard deviations ≤ 3.54%), along with low consumption (0.50 ml sample solution and 25.0 mg adsorbent). Based on the density functional theory, computational simulation was used to make a preliminary prediction for rational design of MIPs and gave a reasonable elaboration involving the potential mechanism of templates interacting with functional monomers. The adsorption kinetics and thermodynamics were investigated to evaluate the recombination process of substrates. In addition, the selectivity of MIPs for S-DABN was obtained by MIP-MTSPE coupled with HPLC, which supports the feasibility of this convenient design process. The proposed method was employed for selective extraction of S-DABN and exhibited promising potential in the application of chiral analysis.


Assuntos
Impressão Molecular , Polímeros , Adsorção , Cromatografia Líquida de Alta Pressão , Diaminas , Naftalenos , Extração em Fase Sólida , Estereoisomerismo
16.
Bioorg Chem ; 106: 104506, 2021 01.
Artigo em Inglês | MEDLINE | ID: mdl-33276980

RESUMO

Thirteen cationic peptidomimetics derived from amino acids bearing an alkyl or ethynylphenyl moiety that mimic the structure of cationic antibacterial peptides were designed and synthesized using a simple coupling reaction of an amino acid with a substituted amine. Antibacterial activities of the resulting peptidomimetics against drug-sensitive bacteria, such as Gram-positive Staphylococcus aureus (S. aureus) and Bacillus subtilis, Gram-negative Escherichia coli (E. coli) and Salmonella enterica, and a drug-resistant bacterium, methicillin-resistant S. aureus (MRSA), were systematically evaluated. Most peptidomimetics show significant broad-spectrum antibacterial activity. A-L-Iso-C12 (isoleucine derivative bearing a dodecyl moiety) show MICs of 2.5 µg/mL against S. aureus and 4 µg/mL against MRSA and A-L-Val-C12 (valine derivative bearing a dodecyl moiety) show MICs of 1.67 µg/mL against E. coli and 8.3 µg/mL against MRSA. A-L-Val-C12 showed low cytotoxicity toward L929 cells in comparison with SGC 7901 cells, indicating tumor-directed killing by peptidomimetics while avoiding toxicity to normal cells. The influences of type of amino acid and substituent, length of substituent, and stereochemistry of amino acids on antibacterial activity and cytotoxicity of peptidomimetics were systematically investigated. The results indicate that this series of cationic peptidomimetics derived from amino acids display antitumor activity and may be useful for treatment of bacterial infections.


Assuntos
Aminoácidos/farmacologia , Antibacterianos/farmacologia , Antineoplásicos/farmacologia , Peptidomiméticos/farmacologia , Aminoácidos/síntese química , Aminoácidos/química , Antibacterianos/síntese química , Antibacterianos/química , Antineoplásicos/síntese química , Antineoplásicos/química , Bacillus subtilis/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Células Cultivadas , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Escherichia coli/efeitos dos fármacos , Humanos , Testes de Sensibilidade Microbiana , Estrutura Molecular , Peptidomiméticos/síntese química , Peptidomiméticos/química , Salmonella enterica/efeitos dos fármacos , Staphylococcus aureus/efeitos dos fármacos , Relação Estrutura-Atividade
17.
BMC Anesthesiol ; 21(1): 312, 2021 12 10.
Artigo em Inglês | MEDLINE | ID: mdl-34893066

RESUMO

BACKGROUND: There is a lack of reports in the literature regarding changes in radial artery blood flow after decannulation. The objective of this study was to investigate changes in radial and ulnar artery blood flow after radial artery decannulation using Doppler ultrasound and to explore the factors that influence radial artery blood flow recovery. METHODS: In current observational study, we used colour Doppler ultrasound to measure the cross-sectional area of the radial (SR) and ulnar artery (SU) and peak systolic velocity of the radial (PSVR) and ulnar artery (PSVU) for both hands at four time points in patients with radial artery cannulation: pre-cannulation (T0), 30 min after decannulation (T1), 24 h after decannulation (T2), and 7 days after decannulation (T3). Repeated measures analysis of variance and logistic regression analysis were performed to analyse the data. RESULTS: Overall, 120 patients were included in the present study. We obtained the following results on the side ipsilateral to the cannulation: compared with T0, the ratio of PSVU/PSVR increased significantly at T1 and T2 (p < 0.01); compared with T1, the ratio of PSVU/PSVR decreased significantly at T2 and T3 (p < 0.01); compared with T2, the ratio of PSVU/PSVR decreased significantly at T3 (p < 0.01). Female sex (OR, 2.76; 95% CI, 1.01-7.57; p = 0.048) and local hematoma (OR 3.04 [1.12-8.25]; p = 0.029) were factors that were significantly associated with the recovery of radial artery blood flow 7 days after decannulation. CONCLUSIONS: There was a compensatory increase in blood flow in the ulnar artery after ipsilateral radial artery decannulation. Female sex and local hematoma formation are factors that may affect the recovery of radial artery blood flow 7 days after catheter removal.


Assuntos
Cateterismo Periférico , Artéria Radial/fisiologia , Artéria Ulnar/fisiologia , Ultrassonografia Doppler em Cores/métodos , Velocidade do Fluxo Sanguíneo/fisiologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Artéria Radial/diagnóstico por imagem , Fluxo Sanguíneo Regional/fisiologia , Artéria Ulnar/diagnóstico por imagem
18.
Molecules ; 26(18)2021 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-34577157

RESUMO

The development of organic polymer materials for disinfection and sterilization is thought of as one of the most promising avenues to solve the growth and spread of harmful microorganisms. Here, a series of linear polyisocyanide quaternary ammonium salts (L-PQASs) with different structures and chain lengths were designed and synthesized by polymerization of phenyl isocyanide monomer containing a 4-chloro-1-butyl side chain followed by quaternary amination salinization. The resultant compounds were characterized by 1H NMR and FT-IR. The antibacterial activity of L-PQASs with different structures and chain lengths against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was evaluated by determining the minimum inhibitory concentrations (MICs). The L-POcQAS-M50 has the strongest antimicrobial activity with MICs of 27 µg/mL against E. coli and 32 µg/mL against S. aureus. When the L-PQASs had the same polymerization degree, the order of the antibacterial activity of the L-PQASs was L-POcQAS-Mn > L-PBuQAS-Mn > L-PBnQAS-Mn > L-PDBQAS-Mn (linear, polyisocyanide quaternary ammonium salt, monomer, n = 50,100). However, when L-PQASs had the same side chain, the antibacterial activity reduced with the increase of the molecular weight of the main chain. These results demonstrated that the antibacterial activity of L-PQASs was dependent on the structure of the main chain and the length of the side chain. In addition, we also found that the L-POcQAS-M50 had a significant killing effect on MK-28 gastric cancer cells.


Assuntos
Antibacterianos/química , Antineoplásicos/química , Poliuretanos/química , Compostos de Amônio Quaternário/química , Antibacterianos/síntese química , Antibacterianos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Escherichia coli/efeitos dos fármacos , Humanos , Isocianatos/química , Espectroscopia de Ressonância Magnética , Testes de Sensibilidade Microbiana , Polimerização , Poliuretanos/síntese química , Poliuretanos/farmacologia , Compostos de Amônio Quaternário/síntese química , Compostos de Amônio Quaternário/farmacologia , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier , Staphylococcus aureus/efeitos dos fármacos , Neoplasias Gástricas/tratamento farmacológico , Neoplasias Gástricas/patologia , Relação Estrutura-Atividade
19.
Pak J Pharm Sci ; 34(5): 1743-1748, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-34803011

RESUMO

The effects of crude extract from the flowers of Trollius chinensis on expressions of mRNA and proteins related to vital genes (TLR 3, TBK 1, IRF 3 and IFN ß) in TLR 3 signaling pathway were investigated in the presence/absence of Polyinosinic acid-polycytidylic acid (PolyI: C) to ascertain the antiviral mechanism of these flowers. Real-time PCR and western blot were applied to determine the expressions of mRNA and proteins, respectively, and immunofluorescence assay was employed to study the effect on IRF 3 distribution between nuclei and cytoplasma. In the absence of PolyI:C, the crude extract reduced the mRNA expression of TLR 3, IRF 3 and IFN ß and the protein expression of TLR 3, and increased the protein expression of IRF 3 and the distribution of IRF 3 in nuclei. In the presence of PolyI:C, the extract reduced the mRNA and protein expressions of TLR 3 and the mRNA expression of IFN ß, meanwhile inhibited the translocation of IRF 3 into nuclei. The antiviral mechanism of the crude extract from the flowers of T. chinensis is to protect the host from inflammatory damage through intervening the TLR 3 signaling pathway and reducing the secretion of inflammatory factors.


Assuntos
Antivirais/farmacologia , Flores/química , Extratos Vegetais/farmacologia , Ranunculaceae/química , Transdução de Sinais/efeitos dos fármacos , Receptor 3 Toll-Like/metabolismo , Animais , Antivirais/química , Sobrevivência Celular , Cães , Regulação da Expressão Gênica/efeitos dos fármacos , Células Madin Darby de Rim Canino , Extratos Vegetais/química , RNA Mensageiro/genética , RNA Mensageiro/metabolismo , Receptor 3 Toll-Like/genética
20.
Phys Chem Chem Phys ; 22(23): 13108-13117, 2020 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-32490501

RESUMO

Adenosine triphosphate (ATP) biomolecules play critial roles in the biomineralization process during the formation of amorphous calcium phosphate composites (ACPC), and ACPC is an important drug carrier due to its significant advantages of biocompatibility and biodegradability. Hence, studying the behavior of ACPC nanodrug carriers is crucial to investigate the structural regulation of biomimetic minerals and calcium phosphate (CaP)-based drug delivery systems. However, it is difficult to probe these interactions using traditional characterization methods. In this paper, XANES analysis together with STXM successfully provided a method to reveal the interaction of ATP and drug molecules with individual mesoporous ACPC. We found that the adenosine and phosphate groups of ATP biomolecules coordinated with Ca2+ and played critical roles in the formation of ACPC; drug molecules with the -COOH groups were linked to Ca2+via carboxylic acid groups primarily by electrostatic interactions, and the N-containing ring structures within the drug molecules also coordinated with Ca2+.


Assuntos
Trifosfato de Adenosina/química , Fosfatos de Cálcio/química , Doxorrubicina/química , Nanocompostos/química , Portadores de Fármacos/química , Sistemas de Liberação de Medicamentos , Hemoglobinas/química , Tamanho da Partícula , Porosidade , Propriedades de Superfície , Espectroscopia por Absorção de Raios X
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