RESUMO
High-performance electrochromic (EC) and electrofluorochromic (EFC) materials have garnered considerable interest due to their diverse applications in smart windows, optoelectronics, optical displays, military camouflage, etc. While many different EC and EFC polymers have been reported, their preparation often requires multiple steps, and their polymer molecular weights are subjected to batch variation. In this work, we prepared two triphenylamine (TPA)-based and two tetraphenylethylene (TPE)-based derivatives functionalized with terminal styryl groups via direct Suzuki coupling with (4-vinylphenyl)boronic acid and vinylboronic acid pinacol ester. The two novel TPE derivatives exhibited green-yellow aggregation-induced emission (AIE). The EC and EFC properties of pre- and post-thermally treated derivatives spin-coated onto ITO-glass substrates were studied. While all four derivatives showed modest absorption changes with applied voltages up to +2.4 V, retaining a high degree of optical transparency, they exhibited obvious EFC properties with the quenching of blue to yellow fluorescence with IOFF/ON contrast ratios of up to 7.0. The findings therefore demonstrate an elegant approach to preparing optically transparent, heat-induced, cross-linkable styryl-functionalized EFC systems.
RESUMO
Hydrochromic materials, which change color in response to moisture, are highly sought-after due to some unique applications such as moisture detection, humidity monitoring, anti-counterfeiting, and sweat-pore mapping. We herein report a new thioxanthene-9-ols/thioxanthylium cations hydrochromic system. The hydrochromic thioxanthylium cations can be generated/regenerated by exposing a chemically stable thioxanthene-9-ol to trifluoroacetic acid (TFA). The intensely colored thioxanthylium cations can be chemically reverted to the colorless thioxanthene-9-ol. Interestingly, the conversion between thioxanthene-9-ol and its cation species was found to be highly reversible in most cases (up to 50 activation-deactivation cycles). The color and moisture-sensitivity of thioxanthylium cations were also validated to be tunable via functionalization of the thioxanthene core with different aliphatic and aromatic groups at its 9 or 2,7-positions. Finally, paper probes were prepared using solution-immersion and inkjet-printing techniques to demonstrate the system's potential applications in humidity sensing and anti-counterfeiting.
RESUMO
In comparison with traditional inorganic electrochromic materials, organic polymers offer advantages such as fast switching speed, flexibility, lightweightness, low cost and nontoxicity, solution-processability, and color tunability. Herein, a series of hyper-branched copolymers are synthesized from triphenylamine and 3,4-ethylenedioxythiophene with different feed ratios via iron(III) chloride (FeCl3 )-mediated oxidative polymerization. The resultant organic-soluble polymers are easily processable and their corresponding electrochromic devices are found to be stable with limited degradation upon 2500 cycles. In addition to their facile synthesis to achieve solution-processable polymers, studies also show that the polymers exhibit multielectrochromic properties and give rise to five colored states upon oxidative-doping by applying an external voltage between 0 and 2.0 V, providing an interesting example of polymers with unique electrochromic switching among up to five colors, from yellow at the neutral state, to pale green, pale purple, orange, and finally gray.
Assuntos
Compostos Férricos , Polímeros , Aminas , TiofenosRESUMO
The discovery of the aggregation-induced emission (AIE) phenomenon in the early 2000s not only has overcome persistent challenges caused by traditional aggregation-caused quenching (ACQ), but also has brought about new opportunities for the development of useful functional molecules. Through the years, AIE luminogens (AIEgens) have been widely studied for applications in the areas of biomedical and biological sensing, chemosensing, optoelectronics, and stimuli responsive materials. Particularly in the application of chemosensing, a myriad of novel AIE-based sensors has been developed to detect different neutral molecular, cationic and anionic species, with a rapid detection time, high sensitivity and high selectivity by monitoring fluorescence changes. This review thus summarises the recent development of AIE-based chemosensors for the detection of anionic species, including halides and halide-containing anions, cyanides, and sulphur-, phosphorus- and nitrogen- containing anions, as well as a few other anionic species, such as citrate, lactate and anionic surfactants.
Assuntos
Ânions/análise , Medições Luminescentes , Ânions/química , Corantes Fluorescentes , Halogênios/análise , Halogênios/química , Medições Luminescentes/métodos , Processos FotoquímicosRESUMO
Two stable boron dipyrromethene (BODIPY)-based antiaromatic macrocycles, Mc-Fur and Mc-Th, were synthesized through a one-pot Knoevenagel condensation reaction between a BODIPY precursor and furan-2,5-dicarboxaldehyde or thiophene-2,5-dicarboxaldehyde, respectively. 1 Hâ NMR spectroscopic characterization of the two macrocycles supported their highly antiaromatic character. The oxidation properties of the two macrocycles were studied through electron spin resonance spectroscopy and UV/Vis absorption spectrophotometry, which suggested the formation of a stable monoradical cation species on first oxidation followed by an aromatic dicationic species on subsequent oxidation. Both molecules have a nearly planar π-conjugated backbone and show a strong tendency to aggregate in solution due to efficient stacking of the antiaromatic macrocycles. Transient absorption and two-photon absorption (TPA) measurements in solution and aggregated states of the macrocycles revealed that aggregation resulted in large enhancement of TPA cross sections and increased excited-state lifetimes, in accordance with the decrease in the antiaromatic character in the aggregated state.
RESUMO
Here we utilized new diagnostic tools in time-dependent density functional theory to explain the trend of intersystem crossing in benzo(bis)-X-diazole based donor-acceptor-donor type molecules. These molecules display a wide range of fluorescence quantum yields and triplet yields, making them excellent candidates for testing the validity of these diagnostic tools. We believe that these tools are cost-effective and can be applied to structurally similar organic chromophores to predict/explain the trends of intersystem crossing, and thus fluorescence quantum yields and triplet yields without the use of complex and expensive multireference configuration interaction or multireference pertubation theory methods.
RESUMO
The zoonotic malaria parasite Plasmodium knowlesi has recently been established in continuous in vitro culture. Here, the Plasmodium falciparum [(3)H]hypoxanthine uptake assay was adapted for P. knowlesi and used to determine the sensitivity of this parasite to chloroquine, cycloguanil, and clindamycin. The data demonstrate that P. knowlesi is sensitive to all drugs, with 50% inhibitory concentrations (IC50s) consistent with those obtained with P. falciparum This assay provides a platform to use P. knowlesi in vitro for drug discovery.
Assuntos
Hipoxantina/metabolismo , Malária/fisiopatologia , Plasmodium knowlesi/metabolismo , Animais , Antimaláricos/farmacologia , Cloroquina/farmacologia , Clindamicina/farmacologia , Concentração Inibidora 50 , Plasmodium falciparum/efeitos dos fármacos , Plasmodium falciparum/metabolismo , Plasmodium falciparum/patogenicidade , Plasmodium knowlesi/efeitos dos fármacos , Proguanil/farmacologia , Triazinas/farmacologiaRESUMO
Cyclotriphosphazene (CP) is a cyclic inorganic compound with the chemical formula N3P3. This unique molecule consists of a six-membered ring composed of alternating nitrogen and phosphorus atoms, each bonded to two chlorine atoms. CP exhibits remarkable versatility and significance in the realm of materials chemistry due to its easy functionalization via facile nucleophilic substitution reactions in mild conditions as well as intriguing properties of resultant final CP-based molecules or polymers. CP has been served as an important building block for numerous functional materials. This review provides a general and broad overview of the synthesis of CP-based small molecules through nucleophilic substitution of hexachlorocyclotriphosphazene (HCCP), and their applications, including flame retardants, liquid crystals (LC), chemosensors, electronics, biomedical materials, and lubricants, have been summarized and discussed. It would be expected that this review would offer a timely summary of various CP-based materials and hence give an insight into further exploration of CP-based molecules in the future.
RESUMO
Converting polystyrene into value-added oxygenated aromatic compounds is an attractive end-of-life upcycling strategy. However, identification of appropriate catalysts often involves laborious and time-consuming empirical screening. Herein, after demonstrating the feasibility of using acridinium salts for upcycling polystyrene into benzoic acid by photoredox catalysis for the first time, we applied low-cost descriptor-based combinatorial in silico screening to predict the photocatalytic performance of a family of potential candidates. Through this approach, we identified a non-intuitive fluorinated acridinium catalyst that outperforms other candidates for converting polystyrene to benzoic acid in useful yields at low catalyst loadings (≤5 mol%). In addition, this catalyst also proved effective with real-life polystyrene waste containing dyes and additives. Our study underscores the potential of computer-aided catalyst design for valorizing polymeric waste into essential chemical feedstock for a more sustainable future.
RESUMO
A series of conjugated polymers bearing thiophene-based donors and pyromellitic diimide (PMDI) acceptor were prepared, and their electrochromic (EC) properties were studied via using fabricated thin-film EC devices. It was observed that structurally regular alternating polymers with fewer (1 and 2) thiophene donors do not exhibit any EC properties while increasing the number of donors eventually led to the emergence of orange-red-to-green colour switching. On this basis, two more random co-polymers containing higher donor-to-acceptor ratios were synthesized to further improve EC switching properties. The two polymers, which bear a PMDI-to-thiophene ratio of ca. 1 : 7 and 1 : 8, revealed orange red-to-blue colour switching and generally improved optical contrasts and switching speeds in both the visible and near infra-red (NIR) region. In addition, the subtle modulation of polymer colour and hue via variation of the number of thiophene donors was evident through colorimetric study. This work therefore demonstrates the potential and possibility of using the PMDI acceptor unit to construct EC-active conjugated polymers, and considerations for future tuning of colour and switching performances.
RESUMO
The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.
RESUMO
Increased use of bioplastics, such as polylactic acid (PLA), helps in reducing greenhouse gas emissions, decreases energy consumption and lowers pollution, but its degradation efficiency has much room for improvement. The degradation rate of electrospun PLA fibers of varying diameters ranging from 0.15 to 1.33 µm is measured during hydrolytic degradation under different pH from 5.5 to 10, and during aerobic biodegradation in seawater supplemented with activated sewage sludge. In hydrolytic conditions, varying PLA fiber diameter had significant influence over percentage weight loss (W%L), where faster degradation was achieved for PLA fibers with smaller diameter. W%L was greatest for PLA-5 > PLA-12 > PLA-16 > PLA-20, with average W%L at 30.7%, 27.8%, 17.2% and 14.3% respectively. While different pH environment does not have a significant influence on PLA degradation, with W%L only slightly higher for basic environments. Similarly biodegradation displayed faster degradation for small diameter fibers with PLA-5 attaining the highest degree of biodegradation at 22.8% after 90 days. Hydrolytic degradation resulted in no significant structural change, while biodegradation resulted in significant hydroxyl end capping products on the PLA surface. Scanning electron microscopy (SEM) imaging of degraded PLA fibers showed a deteriorated morphology of PLA-5 and PLA-12 fibers with increased adhesion structures and irregularly shaped fibers, while a largely unmodified morphology for PLA-16 and PLA-20.
Assuntos
Poliésteres , Poliésteres/química , Hidrólise , Microscopia Eletrônica de VarreduraRESUMO
Exosuits are a relatively new trend in wearable robotics to answer the flaws of their exoskeleton counterparts, but they remain impractical as the lack of rigidity in their frames makes the integration of crucial components into a single unit a challenge. While some simple solutions exist, almost all current research focuses on the output performance of exosuits rather than the needs of potential beneficiaries of this technology. To address this, a novel mechanism of complete portability for exosuits was developed and tested to improve exosuit practicality and adoption. Designed for elbow flexion, the device produced 12.21-13.66Nm of assistive torque and could be mostly concealed by the wearer's clothing without impacting performance. The proof-of-concept design proved successful and demonstrated many advantages over current portability methods, particularly in size and convenience, weighing only 1.7kg. This device provides the sense of normalcy crucial for a technology to seamlessly integrate into the daily lives of its end users. It is extendable and upgradeable with access to advanced materials and manufacturing methods.Clinical Relevance- Exoskeletons are currently the only marketed wearable robotic device for full limb support. This research is the foundation for a new series of exosuits that could drastically enhance the adoptability, accessibility, and versatility of exosuits in physical rehabilitation and general physical enhancement, becoming a superior alternative or addition.
Assuntos
Exoesqueleto Energizado , Robótica , Extremidade Superior , Exame Físico , TorqueRESUMO
The discovery of aggregation-induced emission (AIE) phenomenon in 2001 has had a significant impact on materials development across different research disciplines. AIE-active materials have been widely exploited for various applications in optoelectronics, sensing, biomedical, and stimuli-responsive systems, etc. This is made possible by integrating AIE features with other fields of science and engineering, such as nanoscience and nanotechnology. AIE has been extensively employed, particularly for biomedical applications, such as biosensing, bioimaging, and theranostics. However, development of AIE-based nanotechnology for other applications is comparatively less, although there have been increasing research activities in recent years. Given the significance and potential of the marriage between AIE hallmark and nanotechnology in AIE-active materials development, this review article summarizes and showcases the latest research efforts in AIE-based nanomaterials, including nanomaterials synthesis and their nonbiomedical applications, such as sensing, optoelectronics, functional coatings, and stimuli-responsive systems. A perspective on the outlook of AIE-based nanostructured materials and relevant nanotechnology for nonbiomedical applications will be provided, giving an insight into how to design AIE-active nanostructures as well as their applications beyond the biomedical domain.
Assuntos
Corantes Fluorescentes , Nanoestruturas , Corantes Fluorescentes/química , NanotecnologiaRESUMO
Spent coffee grounds (SCGs) are waste residues arising from the process of coffee brewing and are usually sent to landfills, causing environmental concerns. SCGs contain a considerable amount of fatty acids and is therefore a promising green alternative bio-based phase change material (PCMs) compared to conventional organic and inorganic PCMs. In this study, the extraction of coffee oil from SCGs was conducted using three different organic solvents-ethanol, acetone, and hexane. The chemical composition, chemical, and thermophysical properties of these coffee oil extracts were studied to evaluate their feasibility as a bio-based PCM. Gas chromatography-mass spectroscopy (GC-MS) analysis indicated that coffee oil contains about 60-80 % of fatty acids while the phase transition temperature of the coffee oil extracts is approximately 4.5 ± 0.72 °C, with latent heat values of 51.15 ± 1.46 J/g as determined by differential scanning calorimetry (DSC). Fourier Transform Infrared Spectroscopy (FTIR) and DSC results of coffee oil extracts after thermal cycling revealed good thermal and chemical stability. An application study to evaluate coffee oil extract as a potential cold therapy modality showed that it can maintain temperatures below normal body temperature for up to 46 min. In conclusion, this work exemplifies the potential of SCGs as a promising green and sustainable resource for bio-based PCMs for low-temperature thermal energy storage applications such as cold-chain transportation and cold therapy.
Assuntos
Café , Temperatura Alta , Café/química , Solventes , Ácidos Graxos , Extratos VegetaisRESUMO
Endospore formation by Bacillus subtilis is a complex and dynamic process. One of the major challenges of sporulation is the assembly of a protective, multilayered, proteinaceous spore coat, composed of at least 70 different proteins. Spore coat formation can be divided into two distinct stages. The first is the recruitment of proteins to the spore surface, dependent on the morphogenetic protein SpoIVA. The second step, known as encasement, involves the migration of the coat proteins around the circumference of the spore in successive waves, a process dependent on the morphogenetic protein SpoVID and the transcriptional regulation of individual coat genes. We provide genetic and biochemical evidence supporting the hypothesis that SpoVID promotes encasement of the spore by establishing direct protein-protein interactions with other coat morphogenetic proteins. It was previously demonstrated that SpoVID directly interacts with SpoIVA and the inner coat morphogenetic protein, SafA. Here, we show by yeast two-hybrid and pulldown assays that SpoVID also interacts directly with the outer coat morphogenetic protein, CotE. Furthermore, by mutational analysis, we identified a specific residue in the N-terminal domain of SpoVID that is essential for the interaction with CotE but dispensable for the interaction with SafA. We propose an updated model of coat assembly and spore encasement that incorporates several physical interactions between the principal coat morphogenetic proteins.
Assuntos
Bacillus subtilis/metabolismo , Proteínas de Bactérias/metabolismo , Proteínas de Membrana/metabolismo , Mapeamento de Interação de Proteínas , Esporos Bacterianos/metabolismo , Bacillus subtilis/crescimento & desenvolvimento , Análise Mutacional de DNA , Modelos Biológicos , Ligação Proteica , Esporos Bacterianos/crescimento & desenvolvimento , Técnicas do Sistema de Duplo-HíbridoRESUMO
Malaria, caused by Plasmodium parasites, results in >400,000 deaths annually. There is no effective vaccine, and new drugs with novel modes of action are needed because of increasing parasite resistance to current antimalarials. Histone deacetylases (HDACs) are epigenetic regulatory enzymes that catalyze post-translational protein deacetylation and are promising malaria drug targets. Here, we describe quantitative structure-activity relationship models to predict the antiplasmodial activity of hydroxamate-based HDAC inhibitors. The models incorporate P. falciparum in vitro activity data for 385 compounds containing a hydroxamic acid and were subject to internal and external validation. When used to screen 22 new hydroxamate-based HDAC inhibitors for antiplasmodial activity, model A7 (external accuracy 91%) identified three hits that were subsequently verified as having potent in vitro activity against P. falciparum parasites (IC50 = 6, 71, and 84 nM), with 8 to 51-fold selectivity for P. falciparum versus human cells.
Assuntos
Malária , Parasitos , Animais , Inibidores de Histona Desacetilases/farmacologia , Humanos , Ácidos Hidroxâmicos/farmacologia , Plasmodium falciparum , Relação Quantitativa Estrutura-AtividadeRESUMO
We report here investigation into the genetic basis of mouse hepatitis virus strain 1 (MHV-1) pneumovirulence. Sequencing of the 3' one-third of the MHV-1 genome demonstrated that the genetic organization of MHV-1 was similar to that of other strains of MHV. The hemagglutinin esterase (HE) protein was truncated, and reverse transcription-PCR (RT-PCR) studies confirmed previous work that suggested that the MHV-1 HE is a pseudogene. Targeted recombination was used to select chimeric viruses containing either the MHV-1 S gene or genes encoding all of the MHV-1 structural proteins, on an MHV-A59 background. Challenge studies in mice demonstrated that expression of the MHV-1 S gene within the MHV-A59 background (rA59/S(MHV-1)) increased the pneumovirulence of MHV-A59, and mice infected with this recombinant virus developed pulmonary lesions that were similar to those observed with MHV-1, although rA59/S(MHV-1) was significantly less virulent. Chimeras containing all of the MHV-1 structural genes on an MHV-A59 background were able to reproduce the severe acute respiratory syndrome (SARS)-like pathology observed with MHV-1 and reproducibly increased pneumovirulence relative to rA59/S(MHV-1), but were still much less virulent than MHV-1. These data suggest that important determinants of pneumopathogenicity are contained within the 3' one-third of the MHV-1 genome, but additional important virulence factors must be encoded in the genome upstream of the S gene. The severity of the pulmonary lesions observed correlates better with elevated levels of inflammatory cytokines than with viral replication in the lungs, suggesting that pulmonary disease has an important immunological component.
Assuntos
Pulmão/patologia , Pulmão/virologia , Glicoproteínas de Membrana/fisiologia , Vírus da Hepatite Murina/patogenicidade , Proteínas do Envelope Viral/fisiologia , Fatores de Virulência/fisiologia , Animais , Infecções por Coronavirus/patologia , Infecções por Coronavirus/virologia , Feminino , Ordem dos Genes , Genes Virais , Glicoproteínas de Membrana/genética , Camundongos , Dados de Sequência Molecular , Vírus da Hepatite Murina/genética , Pneumonia Viral/patologia , Pneumonia Viral/virologia , RNA Viral/química , RNA Viral/genética , Recombinação Genética , Análise de Sequência de DNA , Glicoproteína da Espícula de Coronavírus , Proteínas do Envelope Viral/genética , Fatores de Virulência/genéticaRESUMO
Plasmid DNA is one of the indispensable components in molecular biology research and a potential biomaterial for gene therapy and DNA vaccination. Both quality and quantity of extracted plasmid DNA are of the great interests in cloning and subsequent expression of genes in vitro and in vivo for basic research and therapeutic interventions. Bacteria with extremely short generation times are the valuable source of plasmid DNA that can be isolated through a number of existing techniques. However, the current methods have some limitations in isolating high quality plasmid DNA since the multimeric plasmid which is believed to be more efficiently transcribed by RNA polymerase than the monomeric form, is almost lost during the extraction process. Recently, we developed a rapid isolation technique for multimeric plasmid based on generation of a 'protein aggregate' using a zwitterionic detergent and alkali. Here we have investigated the roles of different parameters in the whole extraction process to optimise the production of high quality multimeric plasmid DNA. Moreover, we have showed the advantageous effects of nanoparticles to effectively sediment the 'protein aggregate' for smooth elution of multimeric plasmid DNA from it. Finally, quality assessment study has revealed that the isolated multimeric DNA is at least 10 times more transcriptionally active than the monomeric form isolated by the commercially available Qiaget kit.
Assuntos
Apatitas/química , DNA Bacteriano/isolamento & purificação , Plasmídeos/isolamento & purificação , Compostos de Amônio Quaternário/química , Soluções Tampão , DNA Bacteriano/genética , Escherichia coli/genética , Escherichia coli/crescimento & desenvolvimento , Células HeLa , Humanos , Nanopartículas/química , Plasmídeos/química , Plasmídeos/genética , Transfecção , Transformação BacterianaRESUMO
Transition metal catalysed C-H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of C-C bonds in the construction of pi-conjugated systems, particularly for conjugated polymers, has benefited much from the advances in C-H bond activation chemistry. Compared to conventional transition-metal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve C-H/C-X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves C-H/C-H cross-coupling protocols driven by the activation of monomers' C(sp2 )-H bonds. Furthermore, poly(annulation) via C-H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed C-H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno[3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrole-containing copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed C-H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed C-H activation polymerization to prepare conjugated polymers were discussed and commented.