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Our results indicate that the nanoparticle's coating is detached from the particle's surface inside cells, leading to formation of nanoparticle clusters with a strong TPL. Furthermore, we observed an optically resolved spatial separation of the gold core and the antibody coating of the particles inside cells. We used data from two-photon microscopy, 2P-FLIM, electron microscopy, and in vitro assays to propose a model of interactions of functionalized 5 nm AuNPs with live cells.The variations of microRNA (miRNA) expression can be valuable biomarkers in disease diagnosis and prognosis. However, current miRNA detection techniques mainly rely on reverse transcription and template replication, which suffer from slowness, contamination risk, and sample loss. To address these limitations, here we introduce a cascade toehold-mediated strand displacement reaction (CTSDR) and CRISPR/Cas12a trans-cleavage for highly sensitive fluorescent miRNA sensing, namely CTSDR-Cas12a. In this work, the target miRNA hybridizes with the terminal toehold site of a rationally designed probe and subsequently initiates dynamic CTSDR, leading to enzyme-free target recycling and the production of multiple programmable DNA duplexes. The obtained DNA duplex acts as an activator to trigger Cas12a trans-cleavage, generating significantly amplified fluorescence readout for highly sensitive detection of the miRNA target. Under the optimal conditions, the developed sensing method can detect target miRNA down to 70.28 fM with a wide linear range from 100 fM to 100 pM. In particular, by designing a set of probes and crRNAs, we demonstrate its broad applicability for the detection of six kinds of miRNAs with high sequence specificity. Furthermore, the method can be satisfactorily applied to monitor miR-21 in total RNA extracted from cells and clinical serum samples. Considering the high sensitivity, specificity, universality, and ease of handling, this strategy provides a great potential platform for the detection of miRNA biomarkers in molecular diagnostic practice.Coronavirus is an enveloped RNA virus that causes mild to severe respiratory diseases in humans, including HKU1-CoV, 229E-CoV, NL63-CoV, OC43-CoV, SARS-CoV, MERS-CoV, and SARS-CoV-2. Due to the outbreak of SARS-CoV-2, it is important to identify the patients and investigate their immune responses. Protein microarray is one of the best platforms to profile the antibodies in the blood because of its fast, multiplexed, and sensitive nature. To fully understand the immune responses and biological specificities, this study developed a human coronavirus (HCoV) protein microarray and included all seven human coronaviruses and three influenza viruses. Each protein was printed in triplicate and formed 14 identical blocks per array. The HCoV protein microarray showed high reproducibility and sensitivity to the monoclonal antibodies against spike and nucleocapsid protein with detection limits of 10-200 pg. The HCoV proteins that were immobilized on the array were properly folded and functional by showing interactions with a known human receptor, e.g., ACE2. By profiling the serum IgG and IgA from 32 COVID-19 patients and 36 healthy patients, the HCoV protein microarray demonstrated 97% sensitivity and 97% specificity with two biomarkers. The results also showed the cross-reactivity of IgG and IgA in COVID-19 patients to spike proteins from various coronaviruses, including that from SARS-CoV, HKU1-CoV, and OC43-CoV. Finally, an innate immune protein named surfactant protein D showed broad affinities to spike proteins in all human coronaviruses. Overall, the HCoV protein microarray is multiplexed, sensitive, and specific, which is useful in diagnosis, immune assessment, biological development, and drug screening.Developing an electrochemiluminescence (ECL) coreactant to minimize the biotoxicity and to maximize the enhancement factor is critical to single-cell ECL microscopy. Here, we reported a guanine-rich single-stranded DNA (G-ssDNA)-loaded high-index faceted gold nanoflower (Hi-AuNF) as a synergistic coreactant of Ru(bpy)32+ for single-cell ECL imaging. Because of the excellent catalytic performance and huge specific surface area, Hi-AuNF serves as not only an ECL enhancer but also a carrier for G-ssDNA. Guanine in G-ssDNA specifically reacts with Ru(bpy)32+ through a so-called "catalytic route" and thus significantly enhances the ECL signal of Ru(bpy)32+. To endow targeting ability to the synergistic coreactant, an aptamer of carcinoembryonic antigen (CEA) is incorporated into the G-ssDNA to form G-ssDNA-Apt for the recognition of human breast adenocarcinoma cells, which overexpress CEA on the cytomembrane. Accordingly, the ECL imaging of CEA on the cytomembrane was realized by using the highly selective Hi-AuNF@G-ssDNA-Apt as the probe as well as the luminophore of Ru(bpy)32+. Compared with the common coreactant tripropylamine with high toxicity and volatility, the Hi-AuNF@G-ssDNA-Apt is considered as a high-performance and biocompatible coreactant, providing exciting opportunities in single-cell imaging and detection.Volume expansion hinders conversion-type transition-metal oxides (TMOs) as potential anode candidates for high-capacity lithium-ion batteries. While nanostructuring and nanosizing have been employed to improve the cycling stability of TMOs, we show here that both high initial Coulombic efficiency (ICE) and stable cycling reversibility are achieved in the layered compound Li0.9Nb0.9Mo1.1O6 (L0.9NMO) by inherent properties of the bulk crystal structure. In this model, MoO6 octahedra as active centers react with lithium ions and endow capacity, while a grid composed of NbO6 octahedra effectively suppresses the volume expansion, enhances the conductivity, and supports the structural skeleton from collapse. As a result, bulk L0.9NMO not only delivers a high discharge capacity of 1128 mA h g-1 at 100 mA g-1 with a considerable ICE of 87% but also exhibits long cycling stability and good rate performance (339 mA h g-1 after 500 cycles at 1 A g-1 with an average Coulombic efficiency approaching 100%). The self-confined structure provides a competitive strategy for stable conversion-type lithium storage.Triplet carbenes (TCs) are of great interest due to their magnetic properties and reactivity, which descend from TCs' unique electronic state. However, the reactivity and stability of TCs are usually a trade-off, and it is difficult to achieve both at the same time. In this work, we were able to enhance the thermal stability of a TC species while maintaining its reactivity by confining them in the nanospace of a metal-organic framework (MOF). We synthesized a new MOF using a TC precursor; subsequently, TCs were generated by photostimulation. The TCs generated in the MOF nanospace were detectable up to 170 K, whereas their non-MOF-confined counterparts (bare ligand) could not be detected above 100 K. In addition, the reactivity of TC generated in MOF with O2 was drastically improved compared to that of bare ligand. Our approach is generally applicable to the stabilization of highly reactive species, whose reactivity needs to be preserved.Functional ligands and polymers have frequently been used to yield target-specific bio-nanoconjugates. Herein, we provide a systematic insight into the effect of the chain length of poly(oligo (ethylene glycol) methyl ether acrylate) (POEGMEA) containing polyethylene glycol on the colloidal stability and antibody-conjugation efficiency of nanoparticles. We employed Reversible Addition-Fragmentation Chain Transfer (RAFT) to design diblock copolymers composed of 7 monoacryloxyethyl phosphate (MAEP) units and 6, 13, 35, or 55 OEGMEA units. We find that when the POEGMEA chain is short, the polymer cannot effectively stabilize the nanoparticles, and when the POEGMEA chain is long, the nanoparticles cannot be efficiently conjugated to antibody. In other words, the majority of the carboxylic groups in larger POEGMEA chains are inaccessible to further chemical modification. We demonstrate that the polymer containing 13 OEGMEA units can effectively bind up to 64% of the antibody molecules, while the binding efficiency drops to 50% and 0% for the polymer containing 35 and 55 OEGMEA units. Moreover, flow cytometry assay statistically shows that about 9% of the coupled antibody retained its activity to recognize B220 biomarkers on the B cells. This work suggests a library of stabile, specific, and bioactive lanthanide-doped nanoconjugates for flow cytometry and mass cytometry application.Transition metal catalyzed asymmetric hydrofunctionalization of readily available unsaturated hydrocarbons presents one of the most straightforward and atom-economic protocols to access valuable optically active products. For decades, noble transition metal catalysts have laid the cornerstone in this field, on account of their superior reactivity and selectivity. In recent years, from an economical and sustainable standpoint, first-row, earth-abundant transition metals have received considerable attention, due to their high natural reserves, affordable costs, and low toxicity. Meanwhile, the earth-abundant metal catalyzed hydrofunctionalization reactions have also gained much interest and been investigated gradually. However, since chiral ligand libraries for earth-abundant transition-metal catalysis are limited to date, the development of highly enantioselective versions remains a significant challenge.This Account summarizes our recent efforts in developing suitable chiral ligands for iron and cobalt cataly further demonstrates the synthetic power of these catalytic systems. The chiral enantioenriched products obtained by these methodologies could be potentially utilized in organic synthesis, medicinal chemistry, and materials science. We believe that our continuous efforts in this field would be beneficial to the development of asymmetric earth-abundant metal catalysis.We report the use of the reported Fe-phthalocyanine complex, PcFe (1; Pc = 1,4,8,11,15,18,22,25-octaethoxy-phthalocyanine), to generate PcFe-amine complexes 1-(NH3)2, 1-(MeNH2)2, and 1-(Me2NH)2. Treatment of 1 or 1-(NH3)2 to an excess of the stable aryloxide radical, 2,4,6-tritert-butylphenoxyl radical (tBuArO•), under NH3 resulted in catalytic H atom abstraction (HAA) and C-N coupling to generate the product 4-amino-2,4,6-tritert-butylcyclohexa-2,5-dien-1-one (2) and tBuArOH. Exposing 1-(NH3)2 to an excess of the trityl (CPh3) variant, 2,6-di-tert-butyl-4-tritylphenoxyl radical (TrArO•), under NH3 did not lead to catalytic ammonia oxidation as previously reported in a related Ru-porphyrin complex. However, pronounced coordination-induced bond weakening of both α N-H and β C-H in the alkylamine congeners, 1-(MeNH2)2 and 1-(Me2NH)2, led to multiple HAA events yielding the unsaturated cyanide complex, 1-(MeNH2)(CN), and imine complex, 1-(MeN═CH2)2, respectively. Subsequent C-N bond formation was also observed in the latter upon addition of a coordinating ligand. Detailed computational studies support an alternating mechanism involving sequential N-H and C-H HAA to generate these unsaturated products.Due to the direct band gap nature, extensive studies have been conducted to improve the optical behavior in monolayer transition metal dichalcogenides (TMDCs) with a formula of MX2 (M = Mo, W; X = S, Se, Te). selleck compound One of the strongest modulating agents of optical behavior is a molecular superacid treatment; however, the chemical event has not been unveiled. Also, the engineering protocol for keeping the treatment is immature. In this work, we systematically study the superacid treatment procedures on monolayer molybdenum disulfide (MoS2) and propose that the interaction, a hydrophilic interaction, between the superacid molecule and MoS2 surface would be critical. As a result of the interaction, the superacid molecules spontaneously form an acidic layer with the thickness of several nanometers on the surface. The power-dependent photoluminescence (PL) measurement indicates the edge of MoS2 flake is more effective and electronically modulated by the treatment. By understanding the superacid nanolayer formation by the treatment, we succeeded in maintaining the ultrastrong PL in the superacid-treated MoS2 for more than 30 days in the ambient air by encapsulation with transparent organic polymers.