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1.
J Org Chem ; 89(11): 7408-7416, 2024 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-38787343

RESUMO

A halide-free ionic pair organocatalyst was proposed for the cycloaddition of CO2 into epoxide reactions. Cholinium pyridinolate ionic pairs with three different substitution positions were designed. Under conditions of temperature of 120 °C, pressure of 1 MPa CO2, and catalyst loading of 5 mol %, the optimal catalyst cholinium 4-pyridinolate ([Ch]+[4-OP]-) was employed. After a reaction time of 12 h, styrene oxide was successfully converted into the corresponding cyclic carbonate, and its selectivity was improved to 90%. A series of terminal epoxides were converted into cyclic carbonates within 12 h, with yields ranging from 80 to 99%. The proposed mechanism was verified by 1H NMR and 13C NMR titrations. Cholinium cations act as a hydrogen bond donor to activate epoxides, and pyridinolate anions combine with carbon dioxide to form intermediate carbonate anions that attack epoxides as nucleophiles and lead to ring opening. In summary, a halide-free ionic pair organocatalyst was designed and the catalytic mechanism in the cycloaddition of CO2 into epoxides reactions was proposed.

2.
J Pediatr ; 258: 113408, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-37019333

RESUMO

OBJECTIVES: To determine how advanced genetic analysis methods may help in clinical diagnosis. STUDY DESIGN: We report a combined genetic diagnosis approach for patients with clinical suspicion of genetic liver diseases in a tertiary referral center, using tools either tier 1: Sanger sequencing on SLC2SA13, ATP8B1, ABCB11, ABCB4, and JAG1 genes, tier 2: panel-based next generation sequencing (NGS), or tier 3: whole-exome sequencing (WES) analysis. RESULTS: In a total of 374 patients undergoing genetic analysis, 175 patients received tier 1 Sanger sequencing based on phenotypic suspicion, and pathogenic variants were identified in 38 patients (21.7%). Tier 2 included 216 patients (39 of tier 1-negative patients) who received panel-based NGS, and pathogenic variants were identified in 60 (27.8%). In tier 3, 41 patients received WES analysis, and 20 (48.8%) obtained genetic diagnosis. Pathogenic variants were detected in 6 of 19 (31.6%) who tested negative in tier 2, and a greater detection rate in 14 of 22 (63.6%) patients with deteriorating/multiorgan disease receiving one-step WES (P = .041). The overall disease spectrum is comprised of 35 genetic defects; 90% of genes belong to the functional categories of small molecule metabolism, ciliopathy, bile duct development, and membrane transport. Only 13 (37%) genetic diseases were detected in more than 2 families. A hypothetical approach using a small panel-based NGS can serve as the first tier with diagnostic yield of 27.8% (98/352). CONCLUSIONS: NGS based genetic test using a combined panel-WES approach is efficient for the diagnosis of the highly diverse genetic liver diseases.


Assuntos
Testes Genéticos , Hepatopatias , Humanos , Sequenciamento do Exoma , Hepatopatias/diagnóstico , Hepatopatias/genética , Sequenciamento de Nucleotídeos em Larga Escala/métodos , Mutação
3.
Phys Chem Chem Phys ; 25(8): 5926-5941, 2023 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-36786529

RESUMO

Lowering the operating temperature (450-650 °C) of solid oxide fuel cells (SOFCs) faces the intrinsic challenge of sluggish electrode reaction kinetics in the low temperature (LT) range. To accelerate the electrode reaction rate, many efforts have been put into the optimization of electrode composition and morphology. In this review, we have summarized recent developments of LT-SOFC electrodes, including anode and cathode materials. For anode performance improvement, the internal structure design, fine anode structure, reforming layer addition, and in situ exsolution techniques are introduced and their related functionalities are also explained, respectively. While for the cathode, we focus on the perovskite-type materials because of their superior catalytic performance and relatively good stability. The optimization of perovskite composition, including A site alkali or alkali-earth metal doping and B site variable-valence transition metal doping, is discussed in detail based on their effects on oxygen reduction reaction (ORR). Besides, nanostructure assembly and 3D morphology design are also recent hotspots for cathode research. Finally, we also propose several research directions in this field, hoping to provide guidelines for future research.

4.
Dev Neurosci ; 44(6): 615-628, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36049464

RESUMO

Neural tube defects (NTDs) constitute the second most common congenital malformation of the central nervous system. The pathogenesis of NTDs is not entirely clear. In recent years, microRNAs (miRNAs) have become a hot spot in genetic and developmental biology research. The present study aimed to explore the potential role of miRNA-26a in NTDs and the underlying pathogenesis thereof. First, we found significantly increased miRNA-26a expression in fetuses with NTDs (p < 0.0001), which significantly downregulated EphA2 and ERK1 mRNA and protein expression levels in fetuses with NTDs compared to normal controls (p < 0.01). In addition, a dual-luciferase reporter assay showed that miR-26a negatively regulated EphA2 by directly binding with the 3'-untranslated region of EphA2. Second, the upregulation of miRNA-26a expression increased caspase 3 and 9 protein expression levels (p < 0.01) and decreased EphA2 mRNA and protein expression levels (p < 0.01), as well as ERK1 and SRF protein expression levels (p < 0.01) in mouse neural stem cells (NE-4C) and human astroblastoma cells (U87MG). Furthermore, the upregulation of miRNA-26a inhibited cell proliferation and enhanced apoptosis of NE-4C and U87MG cells (p < 0.05). Similar results were observed with the MAPK inhibitor PD98059 (p < 0.01). These results suggest that miR-26a targets EphA2, modulates phosphorylation of the MAPK/ERK (MEK) pathway, regulates SRF, and participates in regulating nervous cell proliferation and apoptosis. Dysregulation of the aforementioned mechanism may be involved in the pathogenesis of NTDs.


Assuntos
MicroRNAs , Humanos , Camundongos , Animais , MicroRNAs/genética , MicroRNAs/metabolismo , Regulação para Cima , Apoptose , Proliferação de Células , Neurônios/metabolismo
5.
Pediatr Res ; 92(2): 459-465, 2022 08.
Artigo em Inglês | MEDLINE | ID: mdl-34718353

RESUMO

BACKGROUND: L-Asparaginase (L-Asp) is an important therapeutic for childhood acute lymphoblastic leukemia (ALL). Asparaginase-associated pancreatitis (AAP) is a severe complication of L-Asp related to the dosage. We investigated the incidence of, and risk factors for, AAP in pediatric patients with ALL. METHODS: From January 2002 to December 2018, pediatric patients with ALL treated at National Taiwan University Hospital were enrolled in this study. The diagnosis of AAP was based on the criteria of the Ponte di Legno Toxicity Working Group. RESULTS: Of the 353 patients enrolled in this study, 14 (4.0%) developed AAP. The incidence of AAP in ALL patients was significantly higher after treatment with the 2013 protocol compared with the 2002 protocol of the Taiwan Pediatric Oncology Group (9.5% vs. 1.3%). Multivariate analysis showed that a high peak L-Asp dose intensity (>45,000 U/m2/month) and older age at diagnosis (>6.8 years) were independently predictive of AAP development. CONCLUSIONS: The incidence of acute pancreatitis in childhood ALL was correlated more strongly with the peak dose intensity than with the cumulative dose of L-Asp. These results could be used to reduce the treatment-related complications of ALL. IMPACT: L-Asparaginase is an important therapeutic for childhood acute lymphoblastic leukemia, and the accumulated dosage of L-asparaginase is considered as a major risk factor of asparaginase-associated pancreatitis. This article demonstrated that the incidence of pancreatitis correlates with the dose-intensity of L-asparaginase, but not the accumulated dosage. Identification of patient group with high risk of pancreatitis could lead to early diagnosis and reduce the complication. This finding could aid in developing further new protocol or therapeutic strategy design to reduce treatment-related complications and improve clinical outcomes of childhood acute lymphoblastic leukemia.


Assuntos
Antineoplásicos , Pancreatite , Leucemia-Linfoma Linfoblástico de Células Precursoras , Doença Aguda , Asparaginase/efeitos adversos , Criança , Humanos , Pancreatite/induzido quimicamente , Pancreatite/complicações , Pancreatite/epidemiologia , Leucemia-Linfoma Linfoblástico de Células Precursoras/complicações , Leucemia-Linfoma Linfoblástico de Células Precursoras/tratamento farmacológico
6.
Prostate ; 81(10): 618-628, 2021 07.
Artigo em Inglês | MEDLINE | ID: mdl-33949711

RESUMO

BACKGROUND: Prostate cancer (PC) is the second most lethal cancer for men. For metastatic PC, standard first-line treatment is androgen deprivation therapy (ADT). While effective, ADT has many metabolic side effects. Previously, we found in serum metabolome analysis that ADT reduced androsterone sulfate, 3-hydroxybutyric acid, acyl-carnitines but increased serum glucose. Since ADT reduced ketogenesis, we speculate that low-carbohydrate diets (LCD) may reverse many ADT-induced metabolic abnormalities in animals and humans. METHODS: In a multicenter trial of patients with PC initiating ADT randomized to no diet change (control) or LCD, we previously showed that LCD intervention led to significant weight loss, reduced fat mass, improved insulin resistance, and lipid profiles. To determine whether and how LCD affects ADT-induced metabolic changes, we analyzed serum metabolites after 3-, and 6-months of ADT on LCD versus control. RESULTS: We found androsterone sulfate was most consistently reduced by ADT and was slightly further reduced in the LCD arm. Contrastingly, LCD intervention increased 3-hydroxybutyric acid and various acyl-carnitines, counteracting their reduction during ADT. LCD also reversed the ADT-reduced lactic acid, alanine, and S-adenosyl methionine (SAM), elevating glycolysis metabolites and alanine. While the degree of androsterone reduction by ADT was strongly correlated with glucose and indole-3-carboxaldehyde, LCD disrupted such correlations. CONCLUSIONS: Together, LCD intervention significantly reversed many ADT-induced metabolic changes while slightly enhancing androgen reduction. Future research is needed to confirm these findings and determine whether LCD can mitigate ADT-linked comorbidities and possibly delaying disease progression by further lowering androgens.


Assuntos
Antagonistas de Androgênios/uso terapêutico , Antineoplásicos Hormonais/uso terapêutico , Dieta com Restrição de Carboidratos/tendências , Metabolômica/métodos , Neoplasias da Próstata/sangue , Neoplasias da Próstata/terapia , Idoso , Antagonistas de Androgênios/efeitos adversos , Androsterona/análogos & derivados , Androsterona/sangue , Antineoplásicos Hormonais/efeitos adversos , Humanos , Masculino , Pessoa de Meia-Idade
7.
Small ; 16(12): e1901466, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31131987

RESUMO

Nanostructured tin (IV) oxide (SnO2 ) is emerging as an ideal inorganic electron transport layer in n-i-p perovskite devices, due to superior electronic and low-temperature processing properties. However, significant differences in current-voltage performance and hysteresis phenomena arise as a result of the chosen fabrication technique. This indicates enormous scope to optimize the electron transport layer (ETL), however, to date the understanding of the origin of these phenomena is lacking. Reported here is a first comparison of two common SnO2 ETLs with contrasting performance and hysteresis phenomena, with an experimental strategy to combine the beneficial properties in a bilayer ETL architecture. In doing so, this is demonstrated to eliminate room-temperature hysteresis while simultaneously attaining impressive power conversion efficiency (PCE) greater than 20%. This approach highlights a new way to design custom ETLs using functional thin-film coatings of nanomaterials with optimized characteristics for stable, efficient, perovskite solar cells.

8.
Bioorg Med Chem Lett ; 30(21): 127459, 2020 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-32784087

RESUMO

We report herein the synthesis of novel ring-fused pyrazoloamino pyridine/pyrimidine derivatives as potential FAK inhibitors and the evaluation of pharmaceutical activity against five cancer cell lines (MDA-MB-231, BXPC-3, NCI-H1975, DU145 and 786O). Generally, the majority of compounds displayed strong anti-FAK enzymatic potencies (IC50 < 1 nM) and could effectively inhibit several class of cancer cell lines within the concentration of 3 µM in comparison with GSK2256098 as a reference. Among them, compound 4o is considered to be the most effective due to high sensitivity in antiproliferation. In culture, 4o could not only inhibit FAK Y397 phosphorylation in MDA-MB-231 cell line, but also trigger apoptosis in a dose-dependent manner. Furthermore, computational docking analysis also suggested that 4o and TAE-226 displayed the similar interaction with FAK kinase domain.


Assuntos
Antineoplásicos/farmacologia , Desenho de Fármacos , Quinase 1 de Adesão Focal/antagonistas & inibidores , Inibidores de Proteínas Quinases/farmacologia , Piridinas/farmacologia , Pirimidinas/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Quinase 1 de Adesão Focal/metabolismo , Humanos , Estrutura Molecular , Inibidores de Proteínas Quinases/síntese química , Inibidores de Proteínas Quinases/química , Piridinas/química , Pirimidinas/química , Relação Estrutura-Atividade
9.
Acta Cardiol Sin ; 35(3): 320-324, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-31249462

RESUMO

BACKGROUND: Hematoma and skin damage are not uncommon after cardiac implantable electronic device (CIED) placement. The use of conventional hemostatic gauze and tape seems to be suboptimal in controlling these complications. This study aimed to evaluate the impact of a novel compression dress with a special pad and elastic bands for postoperative care. METHODS: A total of 175 CIED recipients were randomly divided into two groups: an experimental group with 85 patients who used a non-taped compression dress and a control group with 90 patients who used conventional gauze ball and elastic tapes. Skin integrity, hematoma, and oozing were compared between these two groups within 7 days after surgery. RESULTS: The mean age of the patients was 71.2 ± 13.3 years, and 83 (47.4%) were male. The results of the experimental vs. control group were as follows: skin integrity - 96.5% vs. 86.7% (p < 0.05); hematoma - 0% vs. 7.8% (p < 0.05); and oozing - 1.2% vs. 7.8% (p < 0.05). All observed endpoints were better in the experimental group. CONCLUSIONS: The use of a non-taped compression dress was associated with less unfavorable outcomes in terms of skin integrity and hemostasis.

10.
Angew Chem Int Ed Engl ; 58(31): 10582-10586, 2019 07 29.
Artigo em Inglês | MEDLINE | ID: mdl-31111993

RESUMO

Lead poisoning is an important problem because of its serious effects on human health. Yet a solution is not available due to an incomplete understanding of the state of lead ions in blood. Since most blood lead binds to hemoglobin (Hb) in red blood cells, identifying and capturing lead-contaminated Hb in RBCs is important. Herein, a magnetic blood lead remover with hyperbranched poly(amidoamine)s (HPAM) as template/co-adsorbent and core-shell mesoporous structure was synthesized. Lead-containing Hb was selectively captured and then fixed by mesoporous channels. The magnetic separation technology was used to separate the magnetic remover from blood. A related blood lead clean-up apparatus was used to remove lead from the blood of a pig in vivo. Results of physical/chemical characterizations, biocompatibility experiments, animal tests, and theoretical simulation verify the safety and efficiency of this removal strategy and the high efficiency of the blood lead clean-up apparatus.


Assuntos
Chumbo/isolamento & purificação , Adsorção , Animais , Hemoglobinas/química , Cinética , Chumbo/sangue , Chumbo/química , Tamanho da Partícula , Poliaminas/sangue , Poliaminas/síntese química , Poliaminas/química , Porosidade , Propriedades de Superfície , Suínos
11.
Langmuir ; 33(21): 5245-5252, 2017 05 30.
Artigo em Inglês | MEDLINE | ID: mdl-28498661

RESUMO

Silicone catheter has been widely used in peritoneal dialysis. The research missions of improving blood compatibility and the ability of resisting bacterial adhesion of silicone catheter have been implemented for the biomedical requirements. However, most of modification methods of surface modification were only able to develop the blood-contacting biomaterials with good hemocompatibility. It is difficult for the biomaterials to resist bacterial adhesion. Here, agarose was selected to resist bacterial adhesion, and heparin was chosen to improve hemocompatibility of materials. Both of them were loaded into mesoporous silica nanoparticles (MSNs), which were successfully modified on the silicone film surface via electrostatic interaction. Structures of the mesoporous coatings were characterized in detail by dynamic light scattering, transmission electron microscopy, Brunauer-Emmett-Teller surface area, thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscope, and water contact angle. Platelet adhesion and aggregation, whole blood contact test, hemolysis and related morphology test of red blood cells, in vitro clotting time tests, and bacterial adhesion assay were performed to evaluate the anticoagulant effect and the ability of resisting bacterial adhesion of the modified silicone films. Results indicated that silicone films modified by MSNs had a good anticoagulant effect and could resist bacterial adhesion. The modified silicone films have potential as blood-contacting biomaterials that were attributed to their biomedical properties.


Assuntos
Nanopartículas , Anticoagulantes , Aderência Bacteriana , Heparina , Adesividade Plaquetária , Porosidade , Sefarose , Dióxido de Silício , Silicones , Espectroscopia de Infravermelho com Transformada de Fourier , Propriedades de Superfície
12.
Phys Chem Chem Phys ; 19(16): 10227-10230, 2017 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-28396893

RESUMO

A composite cathode including N-rGO with homogeneously dispersed perovskite La0.8Sr0.2Co0.8Fe0.2O3 on the surface is studied. Li-O2 batteries with LSCF@N-rGO cathode show better performance than those with LSCF-SP or N-rGO cathode. EIS and morphology analysis indicate that LSCF is beneficial to remold the shape of Li2O2 and catalyze the decomposition of Li2O2.

13.
J Comput Chem ; 37(3): 336-44, 2016 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-26459237

RESUMO

Molecular docking techniques have now been widely used to predict the protein-ligand binding modes, especially when the structures of crystal complexes are not available. Most docking algorithms are able to effectively generate and rank a large number of probable binding poses. However, it is hard for them to accurately evaluate these poses and identify the most accurate binding structure. In this study, we first examined the performance of some docking programs, based on a testing set made of 15 crystal complexes with drug statins for the human 3-hydroxy-3-methylglutaryl coenzyme A reductase (HMGR). We found that most of the top ranking HMGR-statin binding poses, predicted by the docking programs, were energetically unstable as revealed by the high theoretical-level calculations, which were usually accompanied by the large deviations from the geometric parameters of the corresponding crystal binding structures. Subsequently, we proposed a new computational protocol, DOX, based on the joint use of molecular Docking, ONIOM, and eXtended ONIOM (XO) methods to predict the accurate binding structures for the protein-ligand complexes of interest. Our testing results demonstrate that the DOX protocol can efficiently predict accurate geometries for all 15 HMGR-statin crystal complexes without exception. This study suggests a promising computational route, as an effective alternative to the experimental one, toward predicting the accurate binding structures, which is the prerequisite for all the deep understandings of the properties, functions, and mechanisms of the protein-ligand complexes.


Assuntos
Hidroximetilglutaril-CoA Redutases/química , Inibidores de Hidroximetilglutaril-CoA Redutases/química , Simulação de Acoplamento Molecular , Sítios de Ligação , Cristalografia por Raios X , Humanos , Hidroximetilglutaril-CoA Redutases/metabolismo , Inibidores de Hidroximetilglutaril-CoA Redutases/metabolismo , Ligantes , Estrutura Molecular
14.
J Chem Inf Model ; 56(1): 73-81, 2016 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-26669534

RESUMO

In the present study, a series of novel maleimide derivatives were rationally designed and optimized, and their inhibitory activities against cyanobacteria class-II fructose-1,6-bisphosphate aldolase (Cy-FBA-II) and Synechocystis sp. PCC 6803 were further evaluated. The experimental results showed that the introduction of a bigger group (Br, Cl, CH3, or C6H3-o-F) on the pyrrole-2',5'-dione ring resulted in a decrease in the Cy-FBA-II inhibitory activity of the hit compounds. Generally, most of the hit compounds with high Cy-FBA-II inhibitory activities could also exhibit high in vivo activities against Synechocystis sp. PCC 6803. Especially, compound 10 not only shows a high Cy-FBA-II activity (IC50 = 1.7 µM) but also has the highest in vivo activity against Synechocystis sp. PCC 6803 (EC50 = 0.6 ppm). Thus, compound 10 was selected as a representative molecule, and its probable interactions with the surrounding important residues in the active site of Cy-FBA-II were elucidated by the joint use of molecular docking, molecular dynamics simulations, ONIOM calculations, and enzymatic assays to provide new insight into the binding mode of the inhibitors and Cy-FBA-II. The positive results indicate that the design strategy used in the present study is very likely to be a promising way to find novel lead compounds with high inhibitory activities against Cy-FBA-II in the future. The enzymatic and algal inhibition assays suggest that Cy-FBA-II is very likely to be a promising target for the design, synthesis, and development of novel specific algicides to solve cyanobacterial harmful algal blooms.


Assuntos
Desenho de Fármacos , Inibidores Enzimáticos/química , Inibidores Enzimáticos/farmacologia , Frutose-Bifosfato Aldolase/antagonistas & inibidores , Relação Quantitativa Estrutura-Atividade , Synechocystis/enzimologia , Domínio Catalítico , Técnicas de Química Sintética , Inibidores Enzimáticos/síntese química , Inibidores Enzimáticos/metabolismo , Frutose-Bifosfato Aldolase/química , Frutose-Bifosfato Aldolase/metabolismo , Simulação de Acoplamento Molecular , Simulação de Dinâmica Molecular , Pirróis/síntese química , Pirróis/química , Pirróis/metabolismo , Pirróis/farmacologia
15.
Bioorg Med Chem ; 24(6): 1225-30, 2016 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-26860927

RESUMO

1,3,8-Trihydroxynaphthalene reductase (3HNR) is an essential enzymes that is involved in fungal melanin biosynthesis. Based on the structural informations of active site of 3HNR, a series of ß-nitrostyrene compounds were rationally designed and synthesized. The enzymatic activities of these compounds showed that most of them exhibited high inhibitory activities (<5.0 µM) against 3HNR; compound 3-2 exhibit the highest inhibitory activity (IC50=0.29 µM). In particular, some of these compounds had moderate fungicidal activity against Magnaporthe grisea. Compound 3-4 showed high in vivo activities against M. grisea (EC50=9.5 ppm). Furthermore, compound 3-2 was selected as a representative molecule, and the probable binding mode of this compound and the surrounding residues in the active site of 3HNR was elucidated by using molecular dock. The positive results suggest that ß-nitrostyrene derivatives are most likely to be promising leads toward the discovery of novel agent of rice blast.


Assuntos
Antifúngicos/farmacologia , Inibidores Enzimáticos/síntese química , Inibidores Enzimáticos/farmacologia , Proteínas Fúngicas/antagonistas & inibidores , Magnaporthe/efeitos dos fármacos , Magnaporthe/enzimologia , Oxirredutases atuantes sobre Doadores de Grupo CH-CH/antagonistas & inibidores , Estirenos/farmacologia , Antifúngicos/síntese química , Antifúngicos/química , Relação Dose-Resposta a Droga , Inibidores Enzimáticos/química , Proteínas Fúngicas/metabolismo , Testes de Sensibilidade Microbiana , Estrutura Molecular , Oxirredutases atuantes sobre Doadores de Grupo CH-CH/metabolismo , Relação Estrutura-Atividade , Estirenos/síntese química , Estirenos/química
16.
J Comput Chem ; 36(3): 137-45, 2015 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-25363207

RESUMO

Within the framework of the Förster theory, the electronic excitation energy transfer pathways in the cyanobacteria allophycocyanin (APC) trimer and hexamer were studied. The associated physical quantities (i.e., excitation energy, oscillator strength, and transition dipole moments) of the phycocyanobilins (PCBs) located in APC were calculated at time-dependent density functional theory (TDDFT) level of theory. To estimate the influence of protein environment on the preceding calculated physical quantities, the long-range interactions were approximately considered with the polarizable continuum model at the TDDFT level of theory, and the short-range interaction caused by surrounding aspartate residue of PCBs were taken into account as well. The shortest energy transfer time calculated in the framework of the Förster model at TDDFT/B3LYP/6-31+G* level of theory are about 0.10 ps in the APC trimer and about 170 ps in the APC monomer, which are in qualitative agreement with the experimental finding that a very fast lifetime of 0.43-0.44 ps in APC trimers, whereas its monomers lacked any corresponding lifetime. These results suggest that the lifetime of 0.43-0.44 ps in the APC trimers determined by Sharkov et al. was most likely attributed to the energy transfer of α(1) -84 ↔ ß(3) -84 (0.23 ps), ß(1) -84 ↔ α(2) -84 (0.11 ps) or ß(2) -84 ↔ α(3) -84 (0.10 ps). So far, no experimental or theoretical energy transfer rates between two APC trimmers were reported, our calculations predict that the predominate energy transfer pathway between APC trimers is likely to occur from α(3) -84 in one trimer to α(5) -84 in an adjacent trimer with a rate of 32.51 ps.


Assuntos
Biopolímeros/química , Cianobactérias/química , Transferência Ressonante de Energia de Fluorescência , Ficocianina/química , Elétrons , Modelos Moleculares
17.
Carbohydr Polym ; 336: 122128, 2024 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-38670759

RESUMO

Traditional submucosal filling materials frequently show insufficient lifting height and duration during clinical procedures. Here, the anionic polysaccharide polymer sodium carboxymethyl starch and cationic Laponite to prepare a hydrogel with excellent shear-thinning ability through physical cross-linking, so that it can achieve continuous improvement of the mucosal cushion through endoscopic injection. The results showed that the hydrogel (56.54 kPa) had a lower injection pressure compared to MucoUp (68.56 kPa). The height of submucosal lifting height produced by hydrogel was higher than MucoUp, and the height maintenance ability after 2 h was 3.20 times that of MucoUp. At the same time, the hydrogel also showed satisfactory degradability and biosafety, completely degrading within 200 h. The hemolysis rate is as low as 0.76 %, and the cell survival rate > 80 %. Subcutaneous implantation experiments confirmed that the hydrogel showed no obvious systemic toxicity. Animal experiments clearly demonstrated the in vivo feasibility of using hydrogels for submucosal uplift. Furthermore, successful endoscopic submucosal dissection was executed on a live pig stomach, affirming the capacity of hydrogel to safely and effectively facilitate submucosal dissection and mitigate adverse events, such as bleeding. These results indicate that shear-thinning hydrogels have a wide range applications as submucosal injection materials.


Assuntos
Hidrogéis , Amido , Amido/análogos & derivados , Animais , Hidrogéis/química , Hidrogéis/farmacologia , Amido/química , Suínos , Camundongos , Mucosa Gástrica/metabolismo , Ressecção Endoscópica de Mucosa/métodos , Injeções , Humanos , Hemólise/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Silicatos/química
18.
J Comput Chem ; 34(12): 1005-12, 2013 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-23299487

RESUMO

In the present study, the electronic energy transfer pathways in trimeric and hexameric aggregation state of cyanobacteria C-phycocyanin (C-PC) were investigated in term of the Förster theory. The corresponding excited states and transition dipole moments of phycocyanobilins (PCBs) located into C-PC were examined by model chemistry in gas phase at time-dependent density functional theory (TDDFT), configuration interaction-singles (CIS), and Zerner's intermediate neglect of differential overlap (ZINDO) levels, respectively. Then, the long-range pigment-protein interactions were approximately taken into account by using polarizable continuum model (PCM) at TDDFT level to estimate the influence of protein environment on the preceding calculated physical quantities. The influence of the short-range interaction caused by aspartate residue nearby PCBs was examined as well. Only when the protonation of PCBs and its long- and short-range interactions were properly taken into account, the calculated energy transfer rates (1/K) in the framework of Förster model at TDDFT/B3LYP/6-31+G* level were in good agreement with the experimental results of C-PC monomer and trimer. Furthermore, the present calculated results suggested that the energy transfer pathway in C-PC monomer is predominant from ß-155 to ß-84 (1/K = 13.4 ps), however, from α-84 of one monomer to ß-84 (1/K = 0.3-0.4 ps) in a neighbor monomer in C-PC trimer. In C-PC hexamer, an additional energy flow was predicted to be from ß-155 (or α-84) in top trimer to adjacent ß-155 (or α-84) (1/K = 0.5-2.7 ps) in bottom trimer.


Assuntos
Simulação por Computador , Cianobactérias/química , Transferência Ressonante de Energia de Fluorescência , Ficocianina/química , Estrutura Molecular
19.
Appl Microbiol Biotechnol ; 97(17): 7597-605, 2013 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-23775267

RESUMO

Poly(ε-L-lysine) (ε-PL) producer strain Streptomyces albulus PD-1 secreted a novel polymeric substance into its culture broth along with ε-PL. The polymeric substance was purified to homogeneity and identified. Matrix-assisted laser desorption ionization-time of flight mass spectrometry and nuclear magnetic resonance spectroscopy as well as other analytical techniques revealed that the substance was poly(L-diaminopropionic acid) (PDAP). PDAP is an L-α,ß-diaminopropionic acid oligomer linking between amino and carboxylic acid functional groups. The molecular weight of PDAP ranged from 500 to 1500 Da, and no co-polymers composed of L-diaminopropionic acid and L-lysine were present in the culture broth. Compared with ε-PL, PDAP exhibited stronger inhibitory activities against yeasts but weaker activities against bacteria. ε-PL and PDAP co-production was also investigated. Both ε-PL and PDAP were synthesized during the stationary phase of growth, and the final ε-PL and PDAP concentration reached 21.7 and 4.8 g L(-1), respectively, in fed-batch fermentation. Citric acid feeding resulted in a maximum ε-PL concentration of 26.1 g L(-1) and a decrease in the final concentration of PDAP to 3.8 g L(-1). No studies on ε-PL and PDAP co-production in Streptomyces albulus have been reported previously, and inhibition of by-products such as PDAP is potentially useful in ε-PL production.


Assuntos
Lisina/biossíntese , Nylons/metabolismo , Streptomyces/metabolismo , Fermentação , Peso Molecular , Nylons/química , Streptomyces/crescimento & desenvolvimento
20.
Adv Sci (Weinh) ; 10(35): e2304224, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37906090

RESUMO

With the rapid development of novel energy conversion and storage technologies, there is a growing demand for enhanced performance in a wide range of electrocatalysts. Perovskite oxides (ABO3 ) have caused widespread concerns due to their excellent electrocatalytic properties, low cost, stable and reliable performance. In recent years, the research on anion O-site doping of perovskite oxides has been a cynosure, which is considered as a promising route for enhancing performance. However, a systematic review summarizing the research progress of anion-doped perovskite oxides is still lacking. Therefore, this review mainly introduces the elements and strategies of various common anions doped at O-site of perovskite oxides, analyzes their influence on the physical and chemical properties of perovskites, and separately concludes their applications in electrocatalysis. This review will provide ideas and prospects for the development of subsequent anion doping strategies for high performance perovskite oxides.

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