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This work demonstrated the first synthetic application of direct C-H olefinations in the step-saving preparation of various hole-transporting materials (HTM) for efficient perovskite solar cells (PSC). Cross-dehydrogenative couplings of naphthodithiophene (NDT) with vinyl arenes under palladium-catalysis facilely generated various new oligo(hetero)aryls with internal alkenes. Reaction conditions were optimized, which gave the product isolated yields of up to 71 % with high (E)-stereoselectivity. These readily accessible NDT core-based small molecules involving olefin as π-spacers displayed immediate power conversion efficiencies of up to 17.2 % without a device oxidation process that is required for the commercially available spiro-OMeTAD and most other existing HTMs while fabricated in corresponding PSC devices.
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The fluorescence intensity of inorganic CsPbBr3 (CPB) perovskite nanocrystals (NCs) decreases in the presence of O2. In this study, we synthesized CPB NCs with various shapes and sizes for use as optical gas sensing materials. We fabricated O2 gas sensors from the various CPB NCs on several porous and nonporous substrates and examined the effects of the NC shapes and aggregate sizes and the substrate pore size on the device response. Our sensor fabricated from CPB nanocrystals on a porous substrate exhibited the highest response; the porous substrate allowed the rapid diffusion of O2 such that the NC surface was exposed effectively to the gas. Thus, the interfacial interaction between NC surfaces and substrates is a critical factor for consideration when preparing gas sensors with a high response.
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Synthetic organic chemists endeavor to develop new reaction conditions, improve product yields, and enhance atom economy (synthetic methodologies), whereas the material scientists strive to create novel functional molecules/structures, increase device stabilities, and promote power conversion efficiencies via device engineering (organic optoelectronics). However, these two prominent research fields seem to have no intersections. Since joining national central university in 2012, our research philosophy aims to narrow, or rather to bridge the gap between synthetic methodologies and π-functional organic materials. In contrast to using multistep synthetic approaches based on Suzuki- or Stille coupling reactions, this personal account describes various step-saving and viable synthesis-shortcuts developed by our group, to access thiophene-based small molecules for optoelectronic applications. We expect these succinct and user-friendly alternative pathways designed by synthetic chemists would help material scientists to reach their target molecules in a more step-economical manner.
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Estrutura Molecular , HumanosRESUMO
Anaerobiospirillum succiniciproducens is a gram-negative, spiral-shaped anaerobe, that is a rare but potentially lethal cause of bacteremia in humans, particularly in immunocompromised hosts. We reported a 69-year-old HIV-infected male presenting with dysphagia, odynophagia and fulminant pneumonia who died. In addition, in a literature review, we summarized the characteristics of 19 adult patients with A. succiniciproducens bacteremia, which were confirmed by matrix-assisted laser desorption ionization-time of flight mass spectrometry or molecular methods. Among those, the presentation of gastrointestinal conditions was the only independent risk factor for mortality. Clinicians should be aware of this pathogen, especially when a culture is negative but a Gram stain reveals gram-negative spiral-shaped bacteria.
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Anaerobiospirillum/genética , Anaerobiospirillum/isolamento & purificação , Anaerobiospirillum/patogenicidade , Infecções por Bactérias Gram-Negativas/etiologia , Infecções por HIV/sangue , Infecções por HIV/complicações , Infecções por HIV/microbiologia , Idoso , Evolução Fatal , Infecções por Bactérias Gram-Negativas/genética , Infecções por Bactérias Gram-Negativas/mortalidade , Infecções por HIV/mortalidade , Humanos , Masculino , TaiwanRESUMO
Perovskite solar cells (PSCs) have become one of the most promising renewable energy converting devices. However, in order to reach a sufficiently high power conversion efficiency (PCE), the PSCs typically require a high-temperature sintering process to prepare mesostructured TiO2 as an efficient electron transport layer (ETL), which prohibits the PSCs from commercialization in the future. This work investigates a low-temperature synthesis of TiO2 nanocrystals and introduces a two-fluid spray coating process to produce a nanostructured ETL for the following deposition of perovskite layer. The temperature during the whole deposition process can be maintained under 150 °C. Compared to the typical planar TiO2 layer, the perovskite layer fabricated on a nanostructured TiO2 layer shows uniform compactness, preferred orientation, and high crystallinity, leading to reproducible and promising device performance. The detail mechanisms are revealed by the contact angle test, morphology characterization, grazing incident wide angle X-Ray scattering measurement, and space charge limited currents analysis. Finally, optimized device performance can be achieved through adequate Zn doping in the TiO2 layer, demonstrating an average PCE of 19.87% with champion PCE of 21.36%. The efficiency can maintain over 80% of its original value after 3000 h storage in ambient atmosphere. This study suggests a promising approach to offer high-efficiency PSCs using the low-temperature process.
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A variety of push-pull type organic dyes are facilely synthesized through the most atom-economical C-H/C-H dehydrogenative coupling reactions. After comprehensive synthetic optimizations, a broad substrate scope is achieved and functional groups, such as ester, ketone, nitrile, nitro, and triazene are well tolerated. The sensitive aldehyde group required for the conversion into anchoring groups for DSSCs applications is also compatible under present oxidant-containing reaction conditions. Based on this optimum C-H/C-H coupling approach, three new organic sensitizers are readily prepared and submitted to solar cell device fabrications, giving the power conversion efficiency (PCE) up to 4.85%. This work constitutes the first example that connects high atom-efficiency C-H/C-H green catalysis with dye-sensitized solar cell applications.
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It has been a concern that the cobalt redox cannot give a good performance for the dye-sensitized solar cells when it is used with ruthenium dyes. The electron dynamics measurements clarified the electron loss processes, and clarified the cause. The result indicated the direct interaction between the ruthenium dyes with the cobalt redox, and it reduced the charge injection from the triplet state of the dyes to the titanium oxide, and also it increased the electron recombination process with the cobalt redox species. Both the problems of injection and recombination were solved by using the ruthenium dye with alkyl chains keeping a distance between the dye and the cobalt redox.
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Perovskite solar cells (PSCs) have attracted considerable interest owing to their low processing costs and high efficiency. A crucial component of these devices is the electron transport layer (ETL), which plays a key role in extracting and transmitting light-induced electrons, modifying interfaces, and adjusting surface energy levels. This minimizes charge recombination in PSCs, a critical factor in their performance. Among the various ETL materials, titanium dioxide (TiO2) and tin dioxide (SnO2) stand out due to their excellent electron mobility, suitable band alignment, high transparency, and stability. TiO2 is widely used because of its appropriate conduction band position, easy fabrication, and favorable charge extraction properties. SnO2, on the other hand, offers higher electron mobility, better stability under UV illumination, and lower processing temperatures, making it a promising alternative. This paper summarizes the latest advancements in the research of electron transport materials, including material selection and a discussion of electron collection. Additionally, it examines doping techniques that enhance electron mobility and surface modification technologies that improve interface quality and reduce recombination. The impact of these parameters on the performance and passivation behavior of PSCs is also examined. Technological advancements in the ETL, especially those involving TiO2 and SnO2, are currently a prominent research direction for achieving high-efficiency PSCs. This review covers the current state and future directions in ETL research for PSCs, highlighting the crucial role of TiO2 and SnO2 in enhancing device performance.
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In this work, we have successfully synthesized 15 new examples (LLA01-06; LinLi01-10) of small-molecule hole-transporting materials (HTM) using the less explored indolocarbazole (ICbz) as core moiety. Different from previously reported ICbz HTMs, LinLi01-10 exhibit new molecular designs in which 3,4-ethylenedioxythiophene (EDOT) units are inserted as crucial π-spacers and fluorine atoms are introdcued into end-group molecules. These substantially improve the materials solubility and device power conversion efficiencies (PCEs) while fabricated in perovskite solar cells (PSC). More importantly, LinLi01-10 are generated by a sustainable synthetic approach involving the use of straightforward C-H/C-Br couplings as key transformations, thus avoiding additional synthetic transformations including halogenation and borylation reactions called substrate prefunctionalizations usually required in Suzuki reactions. Most HTM molecules can be purified simply by reprecipitations instead of conducting column chromatography. In contrast to LLA01-06 without additional EDOT moieties, PSC devices using LinLi01-10 as hole-transport layers display promising PCEs of up to 17.5 %. Interestingly, PSC devices employing seven of the LinLi01-10 as hole-transport molecules, respectively, are all able to show an immediate >10 % PCE (t=0) without any device oxidation/aging process that is necessary for the commercial spiro-OMeTAD based PSCs.
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A new class of fluorinated cyclopenta[2,1-b:3,4-b']dithiophene (CPDT)-based small molecules, namely YC-oF, YC-mF, and YC-H, are demonstrated as hole-transporting materials (HTMs) for high-performance perovskite solar cells (PSCs). PSCs employing YC-oF as the HTM delivered an excellent efficiency of 22.41% with encouraging long-term stability.
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Quantum dot-sensitized solar cells (QDSCs) constructed using cascade CdS/CdSe sensitizers and the novel tetrapod-like ZnO nanoparticles have been fabricated. The cascade co-sensitized QDSCs manifested good electron transfer dynamics and overall power conversion efficiency, compared to single CdS- or CdSe-sensitized cells. The preliminary CdS layer is not only energetically favorable to electron transfer but behaves as a passivation layer to diminish the formation of interfacial defects during CdSe synthesis. On the other hand, the anisotropic tetrapod-like ZnO nanoparticles, with a high electron diffusion coefficient, can afford a better carrier transport than traditional ZnO nanoparticles. The resultant solar cell yielded an excellent performance with a solar power conversion efficiency of 4.24% under simulated one sun (AM1.5G, 100 mW cm(-2)) illumination.
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In this work, two novel tetra-substituted X-shaped molecules X1 and X2 that were constructed with anthracene as the central core and arylamine as the donor groups have been synthesized. The HTMs X1 and X2 were synthesized in two steps from industrially accessible and moderately reasonable beginning reagents. These new HTMs are described in terms of utilization of light absorption, energy level, thermal properties, hole mobility (µh), and film-forming property. The photovoltaic performances of these HTMs were effectively assessed in perovskite solar cells (PSCs). The devices based on these HTMs accomplished an overall efficiency of 16.10% for X1 and 10.25% for X2 under standard conditions (AM 1.5 G and 100 mW cm-2). This precise investigation provides another perspective on the use of HTMs in PSCs with various device configurations.
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In recent years, additive engineering has received considerable attention for the fabrication of high-performance perovskite solar cells (PSCs). In this study, a non-ionic surfactant, polyoxyethylene (20) sorbitan monolaurate (Tween 20), was added as an additive into the MAPbI3 perovskite layer, and the thermal-assisted blade-coating method was used to fabricate a high-quality perovskite film. The Tween 20 effectively passivated defects and traps in the MAPbI3 perovskite films. Such a film fabricated with an appropriate amount of Tween 20 on the substrate showed a higher photoluminescence (PL) intensity and longer carrier lifetime. At the optimal concentration of 1.0 mM Tween 20, the performance of the PSC was apparently enhanced, and the champion PSC demonstrated a PCE of 18.80%. Finally, this study further explored and compared the effect on the device performance and ambient stability of the MAPbI3 perovskite film prepared by the spin-coating method and the thermal-assisted blade coating.
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Candida auris, a multidrug resistant pathogenic yeast, has spread worldwide and caused several outbreaks in healthcare settings. Here, we report the first case of C. auris candidemia in Taiwan in a patient with a two-month history of hospitalization in Vietnam. We performed further investigation on the isolate from the present case as well as the previously reported C. auris isolate identified from a wound in 2018 in Taiwan, which was the first case reported in Taiwan. Both C. auris isolates were found to be susceptible to fluconazole, amphotericin B, and echinocandins. Additionally, mutations in ERG11 or FKS1 were not detected in either isolate. Microsatellite genotyping revealed that both isolates belonged to the South Asian clade. In recent years, C. auris has emerged as a global concern, and differences in clades and susceptibility patterns mandate further awareness and systematic surveillance.
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Candida auris , Candidíase Invasiva , Antifúngicos/farmacologia , Antifúngicos/uso terapêutico , Candida/genética , Candidíase , Candidíase Invasiva/tratamento farmacológico , Candidíase Invasiva/epidemiologia , Humanos , Testes de Sensibilidade Microbiana , Taiwan/epidemiologiaRESUMO
In most research papers, synthesis of organic hole-transporting materials relies on a key-reaction: Stille cross-couplings. This requires tedious prefunctionalizations including the preparation and treatment of unstable organolithium and toxicity-concern organotin reagents. In contrast to traditional multistep synthesis, this work describes that a series of star-shaped small molecules with a carbazole or phenothiazine core can be efficiently synthesized through a shortcut using optimized direct C-H/C-Br cross-couplings as the key step, thus avoiding dealing with the highly reactive organolithium or the toxic organotin species. Device fabrication of perovskite solar cells employing these molecules (6-13) as hole-transporting layers exhibit promising power conversion efficiencies of up to 17.57%.
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Nowadays, a dye-sensitized solar cell (DSSC) attracts attention to its development widely due to its several advantages, such as simple processes, low costs, and flexibility. In this work, we demonstrate the difference in device structures between small size and large size cells (5 cm × 5 cm, 10 cm × 10 cm and 10 cm × 15 cm). The design of the photoanode and dye-sensitized process plays important roles in affecting the cell efficiency and stability. The effects of the TiO2 electrode, using TiCl4(aq) pretreatment and post-treatment processes, are also discussed, whereas, the open-circuit voltage (Voc), short-circuit current density (Jsc), and module efficiency are successfully improved. Furthermore, the effects on module performances by some factors, such as dye solution concentration, dye soaking temperature, and electrolyte injection method are also investigated. We have demonstrated that the output power of a 5 cm × 5 cm DSSC module increases from 86.2 mW to 93.7 mW, and the module efficiency achieves an outstanding performance of 9.79%. Furthermore, enlarging the DSSC modules to two sizes (10 cm × 10 cm and 10 cm × 15 cm) and comparing the performance with different module designs (C-DSSC and S-DSSC) also provides the specific application of polymer sealing and preparing high-efficiency large-area DSSC modules.
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Norovirus-associated diseases are the most common foodborne illnesses worldwide. Polymerase chain reaction-based methods are the primary diagnostics for clinical samples; however, the high mutation rate of norovirus makes viral amplification and genotyping challenging. Technological advances in mass spectrometry (MS) make it a promising tool for identifying disease markers. Besides, the superior sensitivity of MS and proteomic approaches may enable the detection of all variants. Thus, this study aimed to establish an MS-based system for identifying and typing norovirus. We constructed three plasmids containing the major capsid protein VP1 of the norovirus GII.4 2006b, 2006a, and 2009a strains to produce virus-like particles for use as standards. Digested peptide signals were collected using a nano-flow ultra-performance liquid chromatography mass spectrometry (nano-UPLC/MSE) system, and analyzed by ProteinLynx Global SERVER and TREE-PUZZLE software. Results revealed that the LC/MSE system had an excellent coverage rate: the system detected more than 94% of amino acids of 3.61 femtomole norovirus VP1 structural protein. In the likelihood-mapping analysis, the proportions of unresolved quartets were 2.9% and 4.9% in the VP1 and S domains, respectively, which is superior to the 15.1% unresolved quartets in current PCR-based methodology. In summary, the use of LC/MSE may efficiently monitor genotypes, and sensitively detect structural and functional mutations of noroviruses.
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Infecções por Caliciviridae/virologia , Proteínas do Capsídeo/isolamento & purificação , Norovirus/classificação , Sorotipagem/métodos , Humanos , Japão/epidemiologiaRESUMO
In this study, polycaprolactone (PCL)- and poly(acrylic acid) (PAA)-based electrospun nanofibers were prepared for the carriers of antimicrobials and designed composite nanofiber mats for chronic wound care. The PCL- and PAA-based electrospun nanofibers were prepared through in situ polymerization starting from PCL and acrylic acid (AA). Different amounts of AA were introduced to improve the hydrophilicity of the PCL electrospun nanofibers. A compatibilizer and a photoinitiator were then added to the electrospinning solution to form a grafted structure composed of PCL and PAA (PCL-g-PAA). The grafted PAA was mainly located on the surface of a PCL nanofiber. The optimization of the composition of PCL, AA, compatibilizer, and photoinitiator was studied, and the PCL-g-PAA electrospun nanofibers were characterized through scanning electron microscopy and 1H-NMR spectroscopy. Results showed that the addition of AA to PCL improved the hydrophilicity of the electrospun PCL nanofibers, and a PCL/AA ratio of 80/20 presented the best composition and had smooth nanofiber morphology. Moreover, poly[2 -(tert-butylaminoethyl) methacrylate]-grafted graphene oxide nanosheets (GO-g-PTA) functioned as an antimicrobial agent and was used as filler for PCL-g-PAA nanofibers in the preparation of composite nanofiber mats, which exerted synergistic effects promoted by the antibacterial properties of GO-g-PTA and the hydrophilicity of PCL-g-PAA electrospun nanofibers. Thus, the composite nanofiber mats had antibacterial properties and absorbed body fluids in the wound healing process, thereby promoting cell proliferation. The biodegradation of the PCL-g-PAA electrospun nanofibers also demonstrated an encouraging result of three-fold weight reduction compared to the neat PCL nanofiber. Our findings may serve as guidelines for the fabrication of electrospun nanofiber composites that can be used mats for chronic wound care.
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This study improved quality of CH3NH3PbI3 (MAPbI3) perovskite films by delaying thermal annealing in the spin coating process and introducing KI and I2 to prepare MAPbI3 films that were low in defects for high-efficiency perovskite solar cells. The influences of delayed thermal annealing time after coating the MAPbI3 perovskite layer on the crystallized perovskite, the morphology control of MAPbI3 films, and the photoelectric conversion efficiency of solar cells were investigated. The optimal delayed thermal annealing time was found to be 60 min at room temperature. The effect of KI/I2 additives on the growth of MAPbI3 films and the corresponding optimal delayed thermal annealing time were further investigated. The addition of KI/I2 can improve perovskite crystallinity, and the conductivity and carrier mobility of MAPbI3 films. Under optimized conditions, the photoelectric conversion efficiency of MAPbI3 perovskite solar cells can reach 19.36% under standard AM1.5G solar illumination of 100 mW/cm2.