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1.
Polymers (Basel) ; 15(7)2023 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-37050253

RESUMO

The manufacturing of fiber-reinforced plastics has been linked to the discharge of volatile organic compounds (VOCs), particularly toluene and benzene, which have been identified as posing substantial risks to human health and the environment. To counteract this issue, activated carbons have been suggested as a means of reducing VOC emissions through adsorption. The objective of this study was to investigate the adsorption characteristics of toluene and benzene onto activated carbons produced from coal (AC) and coconut shells (CAC). The study was carried out in an aqueous medium. The findings revealed that the AC sample with higher surface characteristics exhibited a higher adsorption capacity (toluene: 196.0784 mg g-1 and benzene: 181.8182 mg g-1) in comparison to the CAC sample (toluene: 135.1351 mg g-1 and benzene: 116.2791 mg g-1). The superior adsorption performance of AC on both VOCs can be attributed to its higher surface characteristics. The Langmuir model was found to be more appropriate than the Freundlich model, as indicated by the higher coefficient of determination (R2) value of the Langmuir isotherm (avg. R2 = 0.9669) compared to that of the Freundlich isotherm (avg. R2 = 0.9654), suggesting the use of a monolayer adsorption mechanism. The adsorption kinetics of the samples were analyzed using the pseudo-first-order and pseudo-second-order models, and the former was found to be more fitting, indicating that the rate of adsorption is directly proportional to the concentration difference between the solution and the sample surface. The adsorption process was found to be spontaneous and favorable based on the positive value of ΔG_ads. Furthermore, the adsorption process was endothermic and disordered, as indicated by the positive values of ΔH_ads and ΔS_ads. The regeneration efficiency of all the samples was secured more than 95% upon the fifth cycle.

2.
Polymers (Basel) ; 13(22)2021 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-34833301

RESUMO

Copolyurea networks (co-UNs) were synthesized via crosslinking polymerization of a mixture of tetrakis(4-aminophenyl)methane (TAPM) and melamine with hexamethylene diisocyanate (HDI) using the organic sol-gel polymerization method. The subsequent thermal treatment of between 200 and 400 °C induced the sintering of the powdery polyurea networks to form porous frameworks via urea bond rearrangement and the removal of volatile hexamethylene moieties. Incorporating melamine into the networks resulted in a higher nitrogen content and micropore ratio, whereas the overall porosity decreased with the melamine composition. The rearranged network composed of the tetraamine/melamine units in an 80:20 ratio showed the highest carbon dioxide adsorption quantity at room temperature. The results show that optimizing the chemical structure and porosity of polyurea-based networks can lead to carbon dioxide adsorbents working at elevated temperatures.

3.
Ear Hear ; 38(2): e74-e84, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-28225736

RESUMO

OBJECTIVE: Evidence suggests that musicians, as a group, have superior frequency resolution abilities when compared with nonmusicians. It is possible to assess auditory discrimination using either behavioral or electrophysiologic methods. The purpose of this study was to determine if the acoustic change complex (ACC) is sensitive enough to reflect the differences in spectral processing exhibited by musicians and nonmusicians. DESIGN: Twenty individuals (10 musicians and 10 nonmusicians) participated in this study. Pitch and spectral ripple discrimination were assessed using both behavioral and electrophysiologic methods. Behavioral measures were obtained using a standard three interval, forced choice procedure. The ACC was recorded and used as an objective (i.e., nonbehavioral) measure of discrimination between two auditory signals. The same stimuli were used for both psychophysical and electrophysiologic testing. RESULTS: As a group, musicians were able to detect smaller changes in pitch than nonmusician. They also were able to detect a shift in the position of the peaks and valleys in a ripple noise stimulus at higher ripple densities than non-musicians. ACC responses recorded from musicians were larger than those recorded from non-musicians when the amplitude of the ACC response was normalized to the amplitude of the onset response in each stimulus pair. Visual detection thresholds derived from the evoked potential data were better for musicians than non-musicians regardless of whether the task was discrimination of musical pitch or detection of a change in the frequency spectrum of the ripple noise stimuli. Behavioral measures of discrimination were generally more sensitive than the electrophysiologic measures; however, the two metrics were correlated. CONCLUSIONS: Perhaps as a result of extensive training, musicians are better able to discriminate spectrally complex acoustic signals than nonmusicians. Those differences are evident not only in perceptual/behavioral tests but also in electrophysiologic measures of neural response at the level of the auditory cortex. While these results are based on observations made from normal-hearing listeners, they suggest that the ACC may provide a non-behavioral method of assessing auditory discrimination and as a result might prove useful in future studies that explore the efficacy of participation in a musically based, auditory training program perhaps geared toward pediatric or hearing-impaired listeners.


Assuntos
Córtex Auditivo/fisiologia , Potenciais Evocados Auditivos/fisiologia , Música , Discriminação da Altura Tonal/fisiologia , Adulto , Estudos de Casos e Controles , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Fatores de Tempo
4.
Angew Chem Int Ed Engl ; 55(38): 11495-8, 2016 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-27513827

RESUMO

The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three- dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme-loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts.


Assuntos
Enzimas/química , Nanoporos , Biocatálise , Enzimas/metabolismo , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Interações Hidrofóbicas e Hidrofílicas , Lipase/química , Lipase/metabolismo , Ácido Oleico/metabolismo , Polietilenoglicóis/química , Fatores de Tempo
5.
Angew Chem Int Ed Engl ; 55(4): 1318-23, 2016 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-26663348

RESUMO

We demonstrate the synthesis of a microporous covalent-network membrane derived from co-continuous blends of a porogenic urea network and a polyimide (PI). We show that the urea networks in the PI matrix may be thermally rearranged while selectively expelling small molecular fragments, thereby forming a new network bearing reticular microporous molecular pathways. The porous structures enable reverse-selective gas separation, efficiently blocking carbon dioxide to which most polymeric membranes exhibit selective permeability. The proposed method for fabricating microporous organic membranes with highly tunable porosities using a variety of chemical structures and processing parameters is facile and shows promise for the creation of new membrane-based molecular-separation techniques.

6.
ACS Macro Lett ; 4(9): 991-995, 2015 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-35596470

RESUMO

Monolithic molecular separation membranes were prepared by utilizing concentration polarization-induced gelation of a particulate covalent network on a porous support. Polymerization of tetra-amine and di-isocyanate monomers produced a stable dispersion of nanoparticles of urea-bonded networks in organic solvent. As the sols were allowed to pass through the support, the critical gelation point was reached due to concentration polarization via accumulation of relatively larger network particles on the substrate surface, resulting in deposition of a nanoporous gel layer, which, upon drying, turned to a monolithic layer of a covalent network with interconnected pores estimated to be 2-10 nm wide. The resulting membrane filters off solutes larger than 3 nm. Facile control of the structure and thickness of the active layer along with the superior chemical and thermal stability are promising features for solvent-resistant nanofiltration membranes suitable for separation of organic, as well as aqueous, solution mixtures.

8.
J Biol Chem ; 282(18): 13601-9, 2007 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-17314101

RESUMO

Harpins are heat-stable, glycine-rich type III-secreted proteins produced by plant pathogenic bacteria, which cause a hypersensitive response (HR) when infiltrated into the intercellular space of tobacco leaves; however, the biochemical mechanisms by which harpins cause plant cell death remain unclear. In this study, we determined the biochemical characteristics of HpaG, the first harpin identified from a Xanthomonas species, under plant apoplast-like conditions using electron microscopy and circular dichroism spectroscopy. We found that His(6)-HpaG formed biologically active spherical oligomers, protofibrils, and beta-sheet-rich fibrils, whereas the null HR mutant His(6)-HpaG(L50P) did not. Biochemical analysis and HR assay of various forms of HpaG demonstrated that the transition from an alpha-helix to beta-sheet-rich fibrils is important for the biological activity of protein. The fibrillar form of His(6)-HpaG is an amyloid protein based on positive staining with Congo red to produce green birefringence under polarized light, increased protease resistance, and beta-sheet fibril structure. Other harpins, such as HrpN from Erwinia amylovora and HrpZ from Pseudomonas syringae pv. syringae, also formed curvilinear protofibrils or fibrils under plant apoplast-like conditions, suggesting that amyloidogenesis is a common feature of harpins. Missense and deletion mutagenesis of HpaG indicated that the rate of HpaG fibril formation is modulated by a motif present in the C terminus. The plant cytotoxicity of HpaG is unique among the amyloid-forming proteins that occur in several microorganisms. Structural and morphological analogies between HpaG and disease-related amyloidogenic proteins, such as Abeta protein, suggest possible common biochemical characteristics in the induction of plant and animal cell death.


Assuntos
Amiloide/metabolismo , Proteínas da Membrana Bacteriana Externa/metabolismo , Bactérias Gram-Negativas/metabolismo , Nicotiana/metabolismo , Doenças das Plantas , Motivos de Aminoácidos/genética , Amiloide/química , Amiloide/ultraestrutura , Animais , Proteínas da Membrana Bacteriana Externa/química , Proteínas da Membrana Bacteriana Externa/genética , Morte Celular/genética , Bactérias Gram-Negativas/química , Bactérias Gram-Negativas/genética , Bactérias Gram-Negativas/patogenicidade , Mutagênese Sítio-Dirigida , Mutação de Sentido Incorreto , Doenças das Plantas/genética , Doenças das Plantas/microbiologia , Folhas de Planta/metabolismo , Folhas de Planta/microbiologia , Folhas de Planta/ultraestrutura , Homologia Estrutural de Proteína , Nicotiana/microbiologia , Nicotiana/ultraestrutura
9.
Cancer Res ; 65(8): 3162-70, 2005 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-15833846

RESUMO

5-Fluorouracil (5-FU) is widely used for treatment of advanced colorectal cancer. However, it is common for such patients to develop resistance to 5-FU, and this drug resistance becomes a critical problem for chemotherapy. The mechanisms underlying this resistance are largely unknown. To screen for proteins possibly responsible for 5-FU resistance, cells resistant to 5-FU were derived from human colon cancer cell lines and two-dimensional gel electrophoresis-based comparative proteomics was done. Two-dimensional gel electrophoresis data showed there was lower expression of the alpha subunit of mitochondrial F(1)F(0)-ATP synthase (ATP synthase) in 5-FU-resistant cells compared with parent cells. Western blotting showed that expression of other ATP synthase complex subunits was also lower in 5-FU-resistant cell lines and that these resistant cells also showed decreased ATP synthase activity and reduced intracellular ATP content. The ATP synthase inhibitor, oligomycin A, strongly antagonized 5-FU-induced suppression of cell proliferation. When 5-FU sensitivity was compared with ATP synthase activity in six different human colon cancer cell lines, a positive correlation has been found. Furthermore, suppressed ATP synthase d-subunit expression by siRNA transfection increased cell viability in the presence of 5-FU. Bioenergetic dysfunction of mitochondria has been reported as a hallmark of many types of cancers (i.e., down-regulation of ATP synthase beta-subunit expression in liver, kidney, colon, squamous oesophageal, and lung carcinomas, as well as in breast and gastric adenocarcinomas). Our findings show that ATP synthase down-regulation may not only be a bioenergetic signature of colorectal carcinomas but may also lead to cellular events responsible for 5-FU resistance.


Assuntos
Antimetabólitos Antineoplásicos/farmacologia , Neoplasias do Colo/tratamento farmacológico , Neoplasias do Colo/enzimologia , Fluoruracila/farmacologia , Mitocôndrias/enzimologia , ATPases Mitocondriais Próton-Translocadoras/antagonistas & inibidores , Aurovertinas/farmacologia , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Neoplasias do Colo/genética , Regulação para Baixo , Resistencia a Medicamentos Antineoplásicos , Metabolismo Energético , Inibidores Enzimáticos/farmacologia , Humanos , ATPases Mitocondriais Próton-Translocadoras/biossíntese , ATPases Mitocondriais Próton-Translocadoras/genética , Oligomicinas/farmacologia , RNA Interferente Pequeno/genética , Transfecção
10.
J Bacteriol ; 186(18): 6239-47, 2004 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-15342594

RESUMO

HpaG is a type III-secreted elicitor protein of Xanthomonas axonopodis pv. glycines. We have determined the critical amino acid residues important for hypersensitive response (HR) elicitation by random and site-directed mutagenesis of HpaG and its homolog XopA. A plasmid clone carrying hpaG was mutagenized by site-directed mutagenesis, hydroxylamine mutagenesis, and error-prone PCR. A total of 52 mutants were obtained, including 51 single missense mutants and 1 double missense mutant. The HR elicitation activity was abolished in the two missense mutants [HpaG(L50P) and HpaG(L43P/L50P)]. Seven single missense mutants showed reduced activity, and the HR elicitation activity of the rest of the mutants was similar to that of wild-type HpaG. Mutational and deletion analyses narrowed the region essential for elicitor activity to the 23-amino-acid peptide (H2N-NQGISEKQLDQLLTQLIMALLQQ-COOH). A synthetic peptide of this sequence possessed HR elicitor activity at the same concentration as the HpaG protein. This region has 78 and 74% homology with 23- and 27-amino-acid regions of the HrpW harpin domains, respectively, from Pseudomonas and Erwinia spp. The secondary structure of the peptide is predicted to be an alpha-helix, as is the HrpW region that is homologous to HpaG. The predicted alpha-helix of HpaG is probably critical for the elicitation of the HR in tobacco plants. In addition, mutagenesis of a xopA gene yielded two gain-of-function mutants: XopA(F48L) and XopA(F48L/M52L). These results indicate that the 12 amino acid residues between L39 and L50 of HpaG have critical roles in HR elicitation in tobacco plants.


Assuntos
Proteínas da Membrana Bacteriana Externa/genética , Proteínas da Membrana Bacteriana Externa/metabolismo , Proteínas de Bactérias/genética , Análise Mutacional de DNA , Fatores de Virulência/genética , Xanthomonas/genética , Xanthomonas/patogenicidade , Sequência de Aminoácidos , Substituição de Aminoácidos/genética , Substituição de Aminoácidos/fisiologia , Proteínas da Membrana Bacteriana Externa/química , Proteínas de Bactérias/fisiologia , Transporte Biológico , Erwinia/genética , Hidroxilamina/farmacologia , Dados de Sequência Molecular , Mutagênese , Mutagênese Sítio-Dirigida , Mutagênicos/farmacologia , Mutação de Sentido Incorreto , Oligopeptídeos/farmacologia , Reação em Cadeia da Polimerase , Estrutura Secundária de Proteína , Pseudomonas/genética , Deleção de Sequência , Homologia de Sequência , Fatores de Virulência/fisiologia , Xanthomonas/metabolismo
11.
Clin Cancer Res ; 10(12 Pt 1): 4176-84, 2004 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-15217955

RESUMO

PURPOSE: 5-Fluorouracil (5-FU) has been the mainstay treatment for colorectal cancer for the past few decades. However, as with other cancers, development of 5-FU resistance has been a major obstacle in colorectal cancer chemotherapy. The purpose of this study was to gain further understanding of the mechanisms underlying 5-FU resistance in colorectal cancer cells. EXPERIMENTAL DESIGN: A 5-FU-resistant cell line was established from the human colon cancer cell line SNU-769A. Protein extracts from these two cell lines (parent and resistant) were analyzed using comparative proteomics to identify differentially expressed proteins. RESULTS: 5-FU-resistant human colon cancer cells were found to overexpress metabotropic glutamate receptor 4 (mGluR4). Other experiments showed cellular resistance to 5-FU (i.e., cell survival) was altered by the mGluR4 agonist l-2-amino-4-phosphonobutyric acid (L-AP 4), and by the mGluR4 antagonist (S)-amino-2-methyl-4-phosphonobutanoic acid (MAP 4), in that L-AP 4 increased 5-FU resistance in SNU-769A cells, whereas MAP 4 ablated 5-FU resistance in 5-FU-resistant cells. However, there was no significant effect of L-AP 4 or MAP 4 on basal cAMP and thymidylate synthase levels. Interestingly, 5-FU down-regulated mGluR4 expression, and MAP 4 suppressed proliferation in both cell lines. CONCLUSIONS: We here report mGluR4 expression in human colon cancer cell line, which provides further evidence for extra-central nervous system expression of glutamate receptors. Overexpression of mGluR4 may tentatively be responsible for 5-FU resistance and, although activation by agonist promotes cell survival in the presence of 5-FU, decreased mGluR4 expression or inactivation by antagonist contributes to cell death.


Assuntos
Neoplasias do Colo/tratamento farmacológico , Resistencia a Medicamentos Antineoplásicos , Fluoruracila/farmacologia , Receptores de Glutamato Metabotrópico/fisiologia , Aminoácidos/farmacologia , Aminobutiratos/farmacologia , Antimetabólitos Antineoplásicos/farmacologia , Antineoplásicos/farmacologia , Western Blotting , Morte Celular , Linhagem Celular Tumoral , Proliferação de Células , Sobrevivência Celular , Cisplatino/farmacologia , AMP Cíclico/metabolismo , Relação Dose-Resposta a Droga , Regulação para Baixo , Eletroforese em Gel Bidimensional , Agonistas de Aminoácidos Excitatórios/farmacologia , Humanos , Ligantes , Organofosfonatos/farmacologia , Receptores de Glutamato Metabotrópico/metabolismo , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz , Sais de Tetrazólio/farmacologia , Tiazóis/farmacologia , Fatores de Tempo
12.
J Bacteriol ; 185(10): 3155-66, 2003 May.
Artigo em Inglês | MEDLINE | ID: mdl-12730176

RESUMO

We sequenced an approximately 29-kb region from Xanthomonas axonopodis pv. glycines that contained the Hrp type III secretion system, and we characterized the genes in this region by Tn3-gus mutagenesis and gene expression analyses. From the region, hrp (hypersensitive response and pathogenicity) and hrc (hrp and conserved) genes, which encode type III secretion systems, and hpa (hrp-associated) genes were identified. The characteristics of the region, such as the presence of many virulence genes, low G+C content, and bordering tRNA genes, satisfied the criteria for a pathogenicity island (PAI) in a bacterium. The PAI was composed of nine hrp, nine hrc, and eight hpa genes with seven plant-inducible promoter boxes. The hrp and hrc mutants failed to elicit hypersensitive responses in pepper plants but induced hypersensitive responses in all tomato plants tested. The Hrp PAI of X. axonopodis pv. glycines resembled the Hrp PAIs of other Xanthomonas species, and the Hrp PAI core region was highly conserved. However, in contrast to the PAI of Pseudomonas syringae, the regions upstream and downstream from the Hrp PAI core region showed variability in the xanthomonads. In addition, we demonstrate that HpaG, which is located in the Hrp PAI region of X. axonopodis pv. glycines, is a response elicitor. Purified HpaG elicited hypersensitive responses at a concentration of 1.0 micro M in pepper, tobacco, and Arabidopsis thaliana ecotype Cvi-0 by acting as a type III secreted effector protein. However, HpaG failed to elicit hypersensitive responses in tomato, Chinese cabbage, and A. thaliana ecotypes Col-0 and Ler. This is the first report to show that the harpin-like effector protein of Xanthomonas species exhibits elicitor activity.


Assuntos
Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Fatores de Transcrição/metabolismo , Xanthomonas/genética , Xanthomonas/patogenicidade , Sequência de Aminoácidos , Composição de Bases , Sequência Conservada , DNA Intergênico , Dosagem de Genes , Regulação Bacteriana da Expressão Gênica , Variação Genética , Solanum lycopersicum/microbiologia , Dados de Sequência Molecular , Família Multigênica , Mutação , Fenótipo , Regiões Promotoras Genéticas , Homologia de Sequência de Aminoácidos , Nicotiana/microbiologia , Fatores de Transcrição/genética , Virulência/genética
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