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1.
ACS Omega ; 8(2): 1989-2000, 2023 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-36687083

RESUMO

We have designed a new medium bandgap non-fullerene small-molecule acceptor consisting of an IDT donor core flanked with 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]-thiophene-4-ylidene) malononitrile (TC) acceptor terminal groups (IDT-TC) and compared its optical and electrochemical properties with the IDT-IC acceptor. IDT-TC showed an absorption profile from 300 to 760 nm, and it has an optical bandgap of 1.65 eV and HOMO and LUMO energy levels of -5.55 and -3.83 eV, respectively. In contrast to IDT-IC, IDT-TC has an upshifted LUMO energy level, which is advantageous for achieving high open-circuit voltage. Moreover, IDT-TC showed higher crystallinity and high electron mobility than IDT-IC. Using a wide bandgap D-A copolymer P as the donor, we compared the photovoltaic performance of IDT-TC, IDT-IC, and IDT-IC-Cl nonfullerene acceptors (NFAs). Polymer solar cells (PSCs) using P: IDT-TC, P: IDT-IC, and P:IDT-IC-Cl active layers achieved a power conversion efficiency (PCE) of 14.26, 11.56, and 13.34%, respectively. As the absorption profiles of IDT-IC-Cl and IDT-TC are complementary to each other, we have incorporated IDT-TC as the guest acceptor in the P: IDT-IC-Cl active layer to fabricate the ternary (P:IDT-TC: IDT-IC-Cl) PSC, demonstrating a PCE of 16.44%, which is significantly higher than that of the binary BHJ devices. The improvement in PCE for ternary PSCs is attributed to the efficient exploitation of excitons via energy transfer from IDT-TC to IDT-IC-Cl, suitable nanoscale phase separation, compact stacking distance, and more evenly distributed charge transport.

2.
Macromol Rapid Commun ; 43(9): e2200060, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35218257

RESUMO

Two D-A copolymers consisting of fused ring pyrrolo-dithieno-quinoxaline acceptors are synthesized with different donor units, i.e., benzodithiophene (BDT) with alkylthienyl (P134) and 2-ethylhexyloxy (P117) side chains. These copolymers are used as donors and a narrow bandgap acceptor Y6 to fabricate bulk heterojunction polymer solar cell devices. Owing to the strong electron-deficient fused ring pyrrolo-bithieno-quinoxaline and weak alkyl thienyl side chains in BDT, the polymer solar cells (PSCs) based on P134:Y6 attain the power conversion efficiency (PCE) of 15.42%, which is higher than the P117:Y6 counterpart (12.14%). The superior value of PCE for P134:Y6 can be associated with more well-adjusted charge transport, weak charge recombination, proficient exciton generation, and dissociation into free charge carriers and their subsequent charge collection owing to the dense π-π stacking distance and more considerable crystal coherence length for the P134:Y6 thin films. This investigation confirms the great potential of a strong acceptor-weak donor tactic for developing efficient D-A copolymers consists of quinoxaline acceptor for PSCs.

3.
Macromol Rapid Commun ; 43(7): e2100839, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35040533

RESUMO

A new acceptor unit anthra[1,2-b: 4,3-b': 6,7-c'']trithiophene-8,12-dione (А3Т) (A2) is synthesized and used to design D-A1 -D-A2 medium bandgap donor copolymers with same thiophene (D) and A2 units but different A1, i.e., fluorinated benzothiadiazole (F-BTz) and benzothiadiazole (BTz) denoted as P130 and P131, respectively. Their detailed optical and electrochemical properties are examined. The copolymers show good solubility in common organic solvents, broad absorption in the visible spectral region from 300 to 700 nm, and deeper HOMO levels of -5.45 and -5.34 eV for P130 and P131, respectively. Finally, an optimized polymer solar cell (PSC) based on P131 as the donor and narrow bandgap non-fullerene small molecule acceptor Y6 demonstrated a power conversion efficiency (PCE) of >11.13%. To further improve the efficiency of the non-fullerene PSC, the P130 is optimized by introducing a fluorine atom into the BTz unit, F-BTz acceptor unit, and PCE PSC based on P130: Y6 active layer increased to >15.28%, which is higher than that for the non-fluorinated analog P131:Y6. The increase in the PCE for former PSC is attributed to the more crystalline nature and compact π-π stacking distance, leading to more balanced charge transport and reduced charge recombination. These remarkable results demonstrate that A3T-based copolymer P130 with F-BTz as the second acceptor is a promising donor material for high-performance PSCs.

4.
Spectrochim Acta A Mol Biomol Spectrosc ; 184: 235-242, 2017 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-28501744

RESUMO

A new scheme for NH2 detection by means of laser-induced fluorescence (LIF) with excitation around wavelength 385nm, accessible using the second harmonic of a solid-state Alexandrite laser, is presented. Detection of NH2 was confirmed by identification of corresponding lines in fluorescence excitation spectra measured in premixed NH3-air flames and on NH2 radicals generated through NH3 photolysis in a nonreactive flow at ambient conditions. Moreover, spectral simulations allow for tentative NH2 line identification. Dispersed fluorescence emission spectra measured in flames and photolysis experiments showed lines attributed to vibrational bands of the NH2 A2A1←X2B1 transition but also a continuous structure, which in flame was observed to be dependent on nitrogen added to the fuel, apparently also generated by NH2. A general conclusion was that fluorescence interferences need to be carefully considered for NH2 diagnostics in this spectral region. Excitation for laser irradiances up to 0.2GW/cm2 did not result in NH2 fluorescence saturation and allowed for efficient utilization of the available laser power without indication of laser-induced photochemistry. Compared with a previously employed excitation/detection scheme for NH2 at around 630nm, excitation at 385.7nm showed a factor of ~15 higher NH2 signal. The improved signal allowed for single-shot NH2 LIF imaging on centimeter scale in flame with signal-to-noise ratio of 3 for concentrations around 1000ppm, suggesting a detection limit around 700ppm. Thus, the presented approach for NH2 detection provides enhanced possibilities for characterization of fuel-nitrogen combustion chemistry.

5.
Adv Ther ; 32(12): 1263-79, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26660938

RESUMO

INTRODUCTION: This article presents the results of an international, multicenter, randomized, double-masked, placebo-controlled clinical study of Visomitin (Mitotech LLC, Moscow, Russian Federation) eye drops in patients with dry eye syndrome (DES). Visomitin is the first registered (in Russia) drug with a mitochondria-targeted antioxidant (SkQ1) as the active ingredient. METHODS: In this multicenter (10 sites) study of 240 subjects with DES, study drug (Visomitin or placebo) was self-administered three times daily (TID) for 6 weeks, followed by a 6-week follow-up period. Seven in-office study visits occurred every 2 weeks during both the treatment and follow-up periods. Efficacy measures included Schirmer's test, tear break-up time, fluorescein staining, meniscus height, and visual acuity. Safety measures included adverse events, slit lamp biomicroscopy, tonometry, blood pressure, and heart rate. Tolerability was also evaluated. RESULTS: This clinical study showed the effectiveness of Visomitin eye drops in the treatment of signs and symptoms of DES compared with placebo. The study showed that a 6-week course of TID topical instillation of Visomitin significantly improved the functional state of the cornea; Visomitin increased tear film stability and reduced corneal damage. Significant reduction of dry eye symptoms (such as dryness, burning, grittiness, and blurred vision) was also observed. CONCLUSION: Based on the results of this study, Visomitin is effective and safe for use in eye patients with DES for protection from corneal damage. FUNDING: Mitotech LLC.


Assuntos
Compostos de Benzalcônio/uso terapêutico , Síndromes do Olho Seco/tratamento farmacológico , Metilcelulose/uso terapêutico , Soluções Oftálmicas/uso terapêutico , Plastoquinona/uso terapêutico , Adulto , Compostos de Benzalcônio/administração & dosagem , Compostos de Benzalcônio/efeitos adversos , Córnea/metabolismo , Método Duplo-Cego , Combinação de Medicamentos , Feminino , Fluoresceína , Humanos , Masculino , Metilcelulose/administração & dosagem , Metilcelulose/efeitos adversos , Pessoa de Meia-Idade , Soluções Oftálmicas/administração & dosagem , Soluções Oftálmicas/efeitos adversos , Plastoquinona/administração & dosagem , Plastoquinona/efeitos adversos , Lágrimas/metabolismo , Resultado do Tratamento , Acuidade Visual
6.
Am J Phys Anthropol ; 138(1): 62-9, 2009 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-18711739

RESUMO

The purpose of this study was to investigate the impact of economic and cultural change on immune function and psychosocial stress in an indigenous Siberian population. We examined Epstein-Barr virus antibodies (EBV), an indirect biomarker of cell-mediated immune function, in venous whole blood samples collected from 143 Yakut (Sakha) herders (45 men and 98 women) in six communities using a cross-sectional study design. We modeled economic change through the analysis of lifestyle incongruity (LI), calculated as the disparity between socioeconomic status and material lifestyle, computed with two orthogonal scales: market and subsistence lifestyle. EBV antibody level was significantly negatively associated with both a market and a subsistence lifestyle, indicating higher cell-mediated immune function associated with higher material lifestyle scores. In contrast, LI was significantly positively associated with EBV antibodies indicating lower immune function, and suggesting higher psychosocial stress, among individuals with economic status in excess of material lifestyle. Individuals with lower incongruity scores (i.e., economic status at parity with material resources, or with material resources in excess of economic status) had significantly lower EBV antibodies. The findings suggest significant health impacts of changes in material well-being and shifting status and prestige markers on health during the transition to a market economy in Siberia. The findings also suggest that relative, as opposed to absolute, level of economic status or material wealth is more strongly related to stress in the Siberian context.


Assuntos
Sistema Imunitário/imunologia , Estilo de Vida , Adulto , Agricultura , Animais , Animais Domésticos , Cultura , Infecções por Vírus Epstein-Barr/epidemiologia , Infecções por Vírus Epstein-Barr/imunologia , Feminino , Herpesvirus Humano 4/imunologia , Herpesvirus Humano 4/isolamento & purificação , Humanos , Sistema Imunitário/fisiologia , Incidência , Masculino , Grupos Raciais , População Rural , Sibéria/epidemiologia , Fatores Socioeconômicos , Estresse Fisiológico/imunologia , Estresse Fisiológico/fisiologia
7.
Trans R Soc Trop Med Hyg ; 102 Suppl 1: S103-10, 2008 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-19121669

RESUMO

The molecular mechanisms involved in the development of a high level of resistance to a wide range of antimicrobials in Burkholderia pseudomallei and closely related species have not been sufficiently investigated. In the present study, the properties of B. pseudomallei, B. mallei and B. thailandensis mutants with increased resistance to fluoroquinolones and cephalosporins were analysed. Resistance to pefloxacin, ofloxacin and ceftazidime in B. pseudomallei and B. thailandensis was accompanied by an increased resistance to aminoglycosides, beta-lactams, macrolides and chloramphenicol, whereas mutants of B. mallei were characterized by a narrower spectrum of resistance. With the use of the differential display technique, we demonstrated that multiple resistant variants of B. pseudomallei, B. mallei and B. thailandensis had an increased expression of putative efflux transporters belonging to the resistance-nodulation division superfamily and the major facilitator superfamily. With the application of PCR-single-stranded conformational polymorphism (PCR-SSCP) and sequencing, point mutations in gyrA quinolone-resistance determining region were detected in the part of multiple resistant B. pseudomallei and B. mallei mutants. These results indicate that various molecular mechanisms are involved in the development of multiple drug resistance in pathogenic Burkholderia and may be useful for further studying the adaptability of this microorganism and optimization of treatment.


Assuntos
Burkholderia/genética , Resistência Microbiana a Medicamentos/genética , Animais , Antibacterianos/uso terapêutico , Burkholderia/efeitos dos fármacos , Burkholderia/isolamento & purificação , Infecções por Burkholderia/tratamento farmacológico , Burkholderia pseudomallei/efeitos dos fármacos , Burkholderia pseudomallei/genética , Burkholderia pseudomallei/isolamento & purificação , Cefalosporinas/uso terapêutico , Cricetinae , DNA Bacteriano/genética , Fluoroquinolonas/uso terapêutico , Humanos , Dados de Sequência Molecular , Mutação Puntual/genética , Reação em Cadeia da Polimerase , Polimorfismo Conformacional de Fita Simples/genética , Especificidade da Espécie
8.
Trans R Soc Trop Med Hyg ; 102 Suppl 1: S134-9, 2008 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-19121675

RESUMO

Burkholderia mallei and B. pseudomallei are highly pathogenic microorganisms for both humans and animals. Moreover, they are regarded as potential agents of bioterrorism. Thus, rapid and unequivocal detection and identification of these dangerous pathogens is critical. In the present study, we describe the use of an optimized protocol for the early diagnosis of experimental glanders and melioidosis and for the rapid differentiation and typing of Burkholderia strains. This experience with PCR-based identification methods indicates that single PCR targets (23S and 16S rRNA genes, 16S-23S intergenic region, fliC and type III secretion gene cluster) should be used with caution for identification of B. mallei and B. pseudomallei, and need to be used alongside molecular methods such as gene sequencing. Several molecular typing procedures have been used to identify genetically related B. pseudomallei and B. mallei isolates, including ribotyping, pulsed-field gel electrophoresis and multilocus sequence typing. However, these methods are time consuming and technically challenging for many laboratories. RAPD, variable amplicon typing scheme, Rep-PCR, BOX-PCR and multiple-locus variable-number tandem repeat analysis have been recommended by us for the rapid differentiation of B. mallei and B. pseudomallei strains.


Assuntos
Burkholderia mallei/isolamento & purificação , Burkholderia pseudomallei/isolamento & purificação , Mormo/diagnóstico , Melioidose/diagnóstico , Animais , Bioterrorismo , Burkholderia mallei/genética , Burkholderia pseudomallei/genética , Impressões Digitais de DNA , DNA Bacteriano , Mormo/microbiologia , Humanos , Melioidose/microbiologia , Dados de Sequência Molecular , Federação Russa
9.
Proc Natl Acad Sci U S A ; 99(17): 10976-81, 2002 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-12177438

RESUMO

The spontaneous genesis of hydrocarbons that comprise natural petroleum have been analyzed by chemical thermodynamic-stability theory. The constraints imposed on chemical evolution by the second law of thermodynamics are briefly reviewed, and the effective prohibition of transformation, in the regime of temperatures and pressures characteristic of the near-surface crust of the Earth, of biological molecules into hydrocarbon molecules heavier than methane is recognized. For the theoretical analysis of this phenomenon, a general, first-principles equation of state has been developed by extending scaled particle theory and by using the technique of the factored partition function of the simplified perturbed hard-chain theory. The chemical potentials and the respective thermodynamic Affinity have been calculated for typical components of the H-C system over a range of pressures between 1 and 100 kbar (1 kbar = 100 MPa) and at temperatures consistent with those of the depths of the Earth at such pressures. The theoretical analyses establish that the normal alkanes, the homologous hydrocarbon group of lowest chemical potential, evolve only at pressures greater than approximately 30 kbar, excepting only the lightest, methane. The pressure of 30 kbar corresponds to depths of approximately 100 km. For experimental verification of the predictions of the theoretical analysis, a special high-pressure apparatus has been designed that permits investigations at pressures to 50 kbar and temperatures to 1,500 degrees C and also allows rapid cooling while maintaining high pressures. The high-pressure genesis of petroleum hydrocarbons has been demonstrated using only the reagents solid iron oxide, FeO, and marble, CaCO3, 99.9% pure and wet with triple-distilled water.


Assuntos
Carbono , Hidrocarbonetos/química , Hidrogênio , Monossacarídeos/química , Petróleo , Planeta Terra , Temperatura Alta , Pressão , Termodinâmica
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