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Copper catalyzed intramolecular annulation of 2-((2benzylidene-1-phenylhydrazineyl)methyl)pyridine derivatives was described. It was found that Cu(II) is reduced under the reaction condition to Cu(I). Synthesized 1, 2-dihydro [1,2,4] triazinium salt showed fluorescence activity in solid state. On treating with base, an instant increase in fluorescence was observed. A detailed physicochemical assessment underscored the robust DNA-binding prowess of the [1,2,4] triazinium cationic species (C1-C3) via intercalative mechanisms. Notably, binding assays with BSA accentuated the heightened nucleic acid affinity of these cationic species.
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CASE: A 10-year-old, postmenarchal girl presented to the emergency department with a closed, displaced, intercondylar T-type distal humerus fracture. Open reduction and internal fixation was performed 3 days following initial presentation. The patient healed but experienced elbow stiffness in the 7 months following the procedure. Implant removal and capsular release were performed at that time. At the 31-month follow-up, the patient reported satisfactory elbow functionality. CONCLUSION: There is limited literature available discussing optimal management and associated outcomes of intercondylar T-type distal humerus fractures in the young-adolescent population. This report presents a possible method for management of the initial injury and the most common associated complication.
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Fixação Interna de Fraturas , Fraturas do Úmero , Humanos , Feminino , Fraturas do Úmero/cirurgia , Fraturas do Úmero/diagnóstico por imagem , Criança , Fixação Interna de Fraturas/métodos , Lesões no Cotovelo , Articulação do Cotovelo/cirurgia , Articulação do Cotovelo/diagnóstico por imagem , Fraturas Distais do ÚmeroRESUMO
Ribosomal RNA (rRNA) plays a key role in protein synthesis and ribosomal biogenesis. The exclusively used commercial dye for RNA staining is SYTO RNASelect, which works in fixed cells only. To overcome this constraint, we synthesized NIR-emissive, highly photostable, and biocompatible carbon nanodots (CNDs) as a fluorescent biomarker for rRNA. The synthesized CNDs could stain rRNA in both live and fixed cells. We were able to visualize rRNA at different sites in eukaryotic cells using super-resolution microscopy (SRM). The CNDs localized rRNA in the dense fibrillar components (DFCs) of the nucleolus, nuclear membrane, and rough endoplasmic reticulum (RER). The super-resolved hollow ring-structured DFC with an FWHM of 140 nm, nuclear membrane with an FWHM of 120 nm, and ER with an FWHM of 115 nm were observed. We further found a marked contrast between the pre-RNA synthesized in cancer cells and normal cells. We believe that these CNDs have great potential in rRNA imaging and comprehending the complex relationships between rRNA dynamics and basic biological processes, disease development, or drug interactions.
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Carbono , Nucléolo Celular , RNA Ribossômico , Humanos , RNA Ribossômico/química , RNA Ribossômico/metabolismo , Carbono/química , Nucléolo Celular/metabolismo , Pontos Quânticos/química , Microscopia de Fluorescência , Células HeLa , Corantes Fluorescentes/químicaRESUMO
The synthesis of supramolecular polymers with controlled architecture is a grand challenge in supramolecular chemistry. Although living supramolecular polymerization via primary nucleation has been extensively studied for controlling the supramolecular polymerization of small molecules, the resulting supramolecular polymers have typically exhibited one-dimensional morphology. In this report, we present the synthesis of intriguing supramolecular polymer architectures through a secondary nucleation event, a mechanism well-established in protein aggregation and the crystallization of small molecules. To achieve this, we choose perylene diimide with 2-ethylhexyl chains at the imide position as they are capable of forming dormant monomers in solution. Activating these dormant monomers via mechanical stimuli and hetero-seeding using propoxyethyl perylene diimide seeds, secondary nucleation event takes over, leading to the formation of three-dimensional spherical spherulites and scarf-like supramolecular polymer heterostructures, respectively. Therefore, the results presented in this study propose a simple molecular design for synthesizing well-defined supramolecular polymer architectures via secondary nucleation.
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Plasmonic coatings can absorb electromagnetic radiation from visible to far-infrared spectrum for the better performance of solar panels and energy saving smart windows. For these applications, it is important for these coatings to be as thin as possible and grown at lower temperatures on arbitrary substrates like glass, silicon, or flexible polymers. Here, we tune and investigate the plasmonic resonance of titanium nitride thin films in lower thicknesses regime varying from ~ 20 to 60 nm. High-quality crystalline thin films of route-mean-square roughness less than ~ 0.5 nm were grown on a glass substrate at temperature of ~ 200 °C with bias voltage of - 60 V using cathodic vacuum arc deposition. A local surface-enhanced-plasmonic-resonance was observed between 400 and 500 nm, which further shows a blueshift in plasmonic frequency in thicker films due to the increase in the carrier mobility. These results were combined with finite-difference-time-domain numerical analysis to understand the role of thicknesses and stoichiometry on the broadening of electromagnetic absorption.
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The bioconversion of lignocellulosic biomass into novel bioproducts is crucial for sustainable biorefineries, providing an integrated solution for circular economy objectives. The current study investigated a novel microwave-assisted acidic deep eutectic solvent (DES) pretreatment of waste cocoa pod husk (CPH) biomass to extract xylooligosaccharides (XOS). The sequential DES (choline chloride/citric acid, molar ratio 1:1) and microwave (450W) pretreatment of CPH biomass was effective in 67.3% xylan removal with a 52% XOS yield from total xylan. Among different XOS of varying degrees of polymerization, a higher xylobiose content corresponding to 69.3% of the total XOS (68.22 mg/g CPH) from liquid fraction was observed. Enzymatic hydrolysis of residual xylan from pretreated CPH biomass with low commercial xylanase (10 IU/g) concentration yielded 24.2% XOS. The MW-ChCl/citric acid synergistic pretreatment approach holds great promise for developing a cost-effective and environmentally friendly method contributing to the sustainable production of XOS from agricultural waste streams.
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Biomassa , Cacau , Solventes Eutéticos Profundos , Glucuronatos , Micro-Ondas , Oligossacarídeos , Oligossacarídeos/química , Cacau/química , Cacau/metabolismo , Hidrólise , Solventes Eutéticos Profundos/química , Xilanos , Biotecnologia/métodos , Ácidos/química , Solventes/químicaRESUMO
Understanding solvent-solute interactions is essential to designing and synthesising soft materials with tailor-made functions. Although the interaction of the solute with the solvent mixture is more complex than the single solvent medium, solvent mixtures are exciting to unfold several unforeseen phenomena in supramolecular chemistry. Here, we report two unforeseen pathways observed during the hierarchical assembly of cationic perylene diimides (cPDIs) in water and amphiphilic organic solvent (AOS) mixtures. When the aqueous supramolecular polymers (SPs) of cPDIs are injected into AOS, initially kinetically trapped short SPs are formed, which gradually transform into thermodynamically stable high aspect ratio SP networks. Using various experimental and theoretical investigations, we found that this temporal evolution follows two distinct pathways depending on the nature of the water-AOS interactions. If the AOS is isopropanol (IPA), water is released from cPDIs into bulk IPA due to strong hydrogen bonding interactions, which further decreases the monomer concentration of cPDIs (Pathway-1). In the case of dioxane AOS, cPDI monomer concentration further increases as water is retained among cPDIs (Pathway-2) due to relatively weak interactions between dioxane and water. Interestingly, these two pathways are accelerated by external stimuli such as heat and mechanical agitation.
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Ethyl methanesulphonate (EMS), is a widely used chemical mutagen that causes high-frequency germline null mutation by inserting an alkyl group into the nucleotide guanine in eukaryotic cells. The effect of EMS on the dynamics of the aneuploid genome, increased cellular instability, and carcinogenicity in relation to benign and malignant tumors are reported, but the molecular level understanding of morphological changes of higher-order chromatin structure has poorly been understood. This is due to a lack of sufficient resolution in conventional microscopic techniques to see small structures below the diffraction limit. Here, using super-resolution radial fluctuation, a largely fragmented, decompaction, and less dense heterochromatin structure upon EMS treatment to HEK 293A cells without any change in nuclear DNA domains is observed. This result suggests an early stage of carcinogenicity happened due to the point mutation. In addition, the distinct structural changes with an elongated morphology of lysosomes are also observed. On the other hand, fragmented and increased heterogeneous populations with an increased cytoplasmic occupancy of mitochondria are observed.
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Microscopia , Mutação Puntual , Microscopia/métodos , Organelas , DNA/química , HeterocromatinaRESUMO
A series of S-adenosyl-L-homosysteine (SAH) analogs, with modification in the base and sugar moiety, have been designed, synthesized and screened as nsp14 and PLpro inhibitors of severe acute respiratory syndrome corona virus (SARS-CoV-2). The outcomes of ADMET (Adsorption, Distribution, Metabolism, Excretion, and Toxicity) studies demonstrated that the physicochemical properties of all analogs were permissible for development of these SAH analogs as antiviral agents. All molecules were screened against different SARS-CoV-2 targets using molecular docking. The docking results revealed that the SAH analogs interacted well in the active site of nsp14 protein having H-bond interactions with the amino acid residues Arg289, Val290, Asn388, Arg400, Phe401 and π-alkyl interactions with Arg289, Val290 and Phe426 of Nsp14-MTase site. These analogs also formed stable H-bonds with Leu163, Asp165, Arg167, Ser246, Gln270, Tyr274 and Asp303 residues of PLpro proteins and found to be quite stable complexes therefore behaved as probable nsp14 and PLpro inhibitors. Interestingly, analog 3 showed significant in silico activity against the nsp14 N7 methyltransferase of SARS-CoV-2. The molecular dynamics (MD) and post-MD results of analog 3 unambiguously established the higher stability of the nsp14 (N7 MTase):3 complex and also indicated its behavior as probable nsp14 inhibitor like the reference sinefungin. The docking and MD simulations studies also suggested that sinefungin did act as SARS-CoV-2 PLpro inhibitor as well. This study's findings not only underscore the efficacy of the designed SAH analogs as potent inhibitors against crucial SARS-CoV-2 proteins but also pinpoint analog 3 as a particularly promising candidate. All the study provides valuable insights, paving the way for potential advancements in antiviral drug development against SARS-CoV-2.Communicated by Ramaswamy H. Sarma.
HighlightsSAH analogs bearing modified bases and sugar moiety have been synthesized as antivirals against SARS-CoV-2.Molecular dynamics simulation established the stability of ligand-protein complex of analog 3 with nsp14 (N7-MTase) protein of SARS-CoV-2.Molecular docking studies of SAH analogs indicated them as nsp14 N7 methyltranferase as well as the PLpro inhibitors of SARS-CoV-2.The in silico antiviral activity of SAH analogs has been found comparable to the reference drug Sinefungin.
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We report a sustainable resistive-type humidity sensor based on chitosan (CS) film deposited on an interdigitated Ti/Au electrode coated SiO2 substrate using a simple drop cast approach for human health monitoring. The sensor revealed remarkably high sensitivity (5.8 MΩ/%RH), fast response/recovery time (21 s/25 s), low hysteresis (â¼9.3%), excellent reversibility, wide detecting range (11-95% RH), and high selectivity toward water vapor. The calculated associated uncertainty at different %RH indicates the excellent repeatability and stable performance of the sensor. The developed sensor is tested for different human breath patterns, and it is found that the sensor can clearly distinguish between the variations in rate and depth of respiration patterns during normal, fast, deep, and nasal breathing and can monitor for apnea-like situations. The sensor is also utilized to perform noncontact skin humidity sensing. Overall, the developed CS film humidity sensor provides a viable approach for the detection of respiratory disorders and human health issues, detected by skin moisture, in a noninvasive manner.
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Recent years have seen a transition to a sustainable circular economy model that uses agro-industrial waste biomass waste to produce energy while reducing trash and greenhouse gas emissions. Biogas production from lignocellulosic biomass (LCB) is an alternative option in the hunt for clean and renewable fuels. Different approaches are employed to transform the LCB to biogas, including pretreatment, anaerobic digestion (AD), and biogas upgradation to biomethane. To maintain process stability and improve AD performance, machine learning (ML) tools are being applied in real-time monitoring, predicting, and optimizing the biogas production process. An environmental life cycle assessment approach for biogas production systems is essential to calculate greenhouse gas emissions. The current review presents a detailed overview of the utilization of agro-waste for sustainable biogas production. Different methods of waste biomass processing and valorization are discussed that contribute towards developing an efficient agro-waste to biogas-based circular economy.
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Resíduos de Alimentos , Gases de Efeito Estufa , Resíduos Industriais , Biocombustíveis , BiomassaRESUMO
Herein, we report new red emissive highly photostable and water-soluble carbon nanodots (TPP CNDs) to visualize mitochondrial dynamics using super-resolution radial fluctuations (SRRF) microscopy. The TPP CNDs were synthesized in a one-step method, using 3-(carboxypropyl)triphenylphosphonium bromide (TPP) and o-phenylenediamine (OPDA) as precursors. The obtained crystal structure, NMR, and mass data suggested the presence of [3-(1H-benzimidazol-2-yl)propyl](triphenyl)phosphonium bromide (C28H26N2P+Br-) as a molecular fluorophore (MF) on the surface of the TPP CNDs. The TPP CNDs showed better photostability than the commercially available MitoTracker™ Green and were highly capable for long-term imaging of mitochondrial fission during hyperglycemic conditions and structural changes upon an antidiabetic drug treatment, without altering their fluorescence nature.
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Brometos , Carbono , Carbono/química , Corantes Fluorescentes/química , Microscopia de Fluorescência/métodos , MitocôndriasRESUMO
Protein-conjugated coinage metal nanoclusters have become promising materials for optoelectronics and biomedical applications. However, the origin of the photoluminescence, especially the long-lived excited state emission in these metal nanoclusters, is still elusive. Here, we unveiled the underlying mechanism of long-lived emission in albumin protein-conjugated copper nanoclusters (Cu NCs) using steady state and time-resolved spectroscopic techniques. Our findings reveal room-temperature phosphorescence (RTP) in protein-conjugated Cu NCs. Time-resolved area-normalized spectra distinguished short- and long-lived components, where the former arises from the singlet state and the latter from the triplet state, thus resulting in RTP. The similarity of the emission spectra at room (298 K) and cryogenic (77 K) temperature ascertains the RTP phenomenon by harvesting the higher-lying triplet states. Time-gated bioimaging of A549 cells using the long-lived emission not only supports RTP emission in the cellular environment but also provides exciting avenues in long-term bioimaging using bovine serum albumin-conjugated Cu NCs.
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Cobre , Cobre/química , Análise EspectralRESUMO
Irritable bowel syndrome (IBS) is a chronic functional disorder which alters gastrointestinal (GI) functions, thus leading to compromised health status. Pathophysiology of IBS is not fully understood, whereas abnormal gut brain axis (GBA) has been identified as a major etiological factor. Recent studies are suggestive for visceral hyper-sensitivity, altered gut motility and dysfunctional autonomous nervous system as the main clinical abnormalities in IBS patients. Bidirectional signalling interactions among these abnormalities are derived through various exogenous and endogenous factors, such as microbiota population and diversity, microbial metabolites, dietary uptake, and psychological abnormalities. Strategic efforts focused to study these interactions including probiotics, antibiotics and fecal transplantations in normal and germ-free animals are clearly suggestive for the pivotal role of gut microbiota in IBS etiology. Additionally, neurotransmitters act as communication tools between enteric microbiota and brain functions, where serotonin (5-hydroxytryptamine) plays a key role in pathophysiology of IBS. It regulates GI motility, pain sense and inflammatory responses particular to mucosal and brain activity. In the absence of a better understanding of various interconnected crosstalks in GBA, more scientific efforts are required in the search of novel and targeted therapies for the management of IBS. In this review, we have summarized the gut microbial composition, interconnected signalling pathways and their regulators, available therapeutics, and the gaps needed to fill for a better management of IBS.
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[This corrects the article DOI: 10.1039/D3RA00752A.].
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The idea of environment friendly and affordable renewable energy resources has prompted the industry to focus on the set up of biorefineries for sustainable bioeconomy. Lignocellulosic biomass (LCB) is considered as an abundantly available renewable feedstock for the production of biofuels which can potentially reduce the dependence on petrochemical refineries. By utilizing various conversion technologies, an integrated biorefinery platform of LCB can be created, embracing the idea of the 'circular bioeconomy'. The development of effective pretreatment methods and biocatalytic systems by various bioengineering and machine learning approaches could reduce the bioprocessing costs, thereby making biomass-based biorefinery more sustainable. This review summarizes the development and advances in the lignocellulosic biorefineries from the LCB to the final product stage using various different state-of-the-art approaches for the progress of circular bioeconomy. The life cycle assessment which generates knowledge on the environmental impacts related to biofuel production chains is also summarized.
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Biocombustíveis , Lignina , Biomassa , BioengenhariaRESUMO
We report an infrared (IR) sensitive mixed phase of V7O16 and V2O5 thin films, grown by cathodic vacuum arc-deposition on glass substrates at relatively low temperatures. We have found that the mixed phase of V7O16 and V2O5 can be stabilized by post-annealing of amorphous VxOy between 300-400 °C, which gets fully converted into V2O5 after annealing at higher temperatures â¼450 °C. The local conversion from VxOy to V2O5 has also been demonstrated by applying different laser powers in Raman spectroscopy measurements. The optical transmission of these films increases as the content of V2O5 increases but the electrical conductivity and the optical bandgap decrease. These results are explained by the role of defects (oxygen vacancies) through the photoluminescence (PL) and time-resolved photoluminescence (TRPL) measurements. The IR sensitivity of the mixed phase is explained by the plasmonic absorption by the V7O16 degenerate semiconductor.
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Double post-synthetic modification is used for the π-extension of perylene based conjugated porous polymers (CPPs) using sequential annulative π-extension (APEX) reactions. This approach enabled us to synthesize new CPPs rendered with donor-acceptor rigid π-systems such as benzoperylene anhydride (BPA-CPP) and benzoperylene benzimidazole (BPBI-CPP) with distinct optical properties. Despite its low surface area, BPBI-CPP shows good CO2 uptake and pH responsive behaviour owing to the presence of benzimidazole rings.
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Coordination complexes offer great potential as cellular imaging probes, which allow to examine specific cell organelle structures in their physiological conditions to better understand the biological system. Understanding the heterogeneous nature of the cell membrane could unveil details of their functionality. Here, we have developed a new anthracene conjugated fluorescent palladium(II) cyclometallate [PdL1Cl] where L1Hâ¯=â¯[2-(2- (anthracen-9-ylmethylene)-1-phenylhydrazineyl)pyridine] (H stands for dissociable proton), which not only specifically stains the cell membrane, but could be utilized to visualise the membrane by the confocal and fluorescence lifetime imaging microscopy (FLIM). This probe is unable to enter inside the cell as it did not pass through the cell membrane via diffusion or various organic and metal transporters. However, the great lipophilicity of fluorescein improves the interaction of the probe with the peptidoglycan layer of the cell membrane. Probable dissociation of chloride ion and formation of positively charged palladium complex resulted in staining the negatively charged cell membrane. The 3D confocal imaging clearly expressed sole membrane staining by the probe. The probe efficiently stains both cancer cells (HeLa and MCF-7 cell lines) and normal cell (HEK 293â¯T), confirming the universality of the probe in membrane staining.
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Corantes Fluorescentes , Paládio , Humanos , Corantes Fluorescentes/química , Paládio/química , Células HEK293 , Imagem Óptica/métodos , Membrana Celular/metabolismoRESUMO
COVID-19, a dreaded and highly contagious pandemic, is flagrantly known for its rapid prevalence across the world. Till date, none of the treatments are distinctly accessible for this life-threatening disease. Under the prevailing conditions of a medical emergency, one creative strategy for the identification of novel and potential antiviral agents gaining momentum in research institutions and progressively being leveraged by pharmaceutical companies is target-based drug repositioning/repurposing. Continuous monitoring and recording of results offer anticipation that this strategy may help to reveal new medications for viral infections. This review recapitulates the neoteric illation of COVID-19, its genomic dispensation, molecular evolution via phylogenetic assessment, drug targets, the most frequently worldwide used repurposed drugs and their therapeutic applications, and a recent update on vaccine management strategies. The available data from solidarity trials exposed that the treatment with several known drugs, viz. lopinavir-ritonavir, chloroquine, hydroxychloroquine, etc. had displayed various antagonistic effects along with no impactful result in the diminution of mortality rate. The drugs, like remdesivir, favipiravir, and ribavirin, have proved to be quite safer therapeutic options for treatment against COVID-19. Similarly, dexamethasone, convalescent plasma therapy and oral administration of 2DG are expected to reduce the mortality rate of COVID-19 patients.