查看更多>>摘要：A new and convenient calculation method based on Rice-Ramsperger-Kassel-Marcus (RRKM) theory assuming an extremely loose transition state (LTS) has been attempted to predict the branching ratio in photodissociation. This method enables estimation of the branching ratios without detailed structural information on the transition state which is indispensable in conventional RRKM calculations. To evaluate our simple method through comparison to the experimental results, photodissociation of 1-bromo-3-chlorobenzene cation (3BCB+) was chosen as a model unimolecular reaction system which has two distinct photodissociation channels in ultraviolet region: 3BCB(+) -> Br-dissociated daughter ion (ClBz(+)) + Br-center dot and 3BCB(+) -> Cl-dissociated daughter ion (BrBz(+)) + Cl-center dot. The branching ratio was monitored with decreasing the internal energy using a linear tandem time-of-flight mass spectrometer, which clearly showed decreased branching ratios of 3BCB(+) -> ClBz(+) + Br-center dot over 3BCB(+) -> BrBz(+) + Cl-center dot in reasonable agreement with the calculation results employing the new method. Although there was some discrepancy in internal energy between the experimental and calculation results, the new calculation method is worth to be extended to other diverse systems considering its intuitive and simple nature. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：The behavior of ethanol oxidation reaction on composite electrodes prepared by deposition platinum on a gold surface (Pt/Au) were studied by cyclic voltammetry and surface enhanced infrared absorption spectroscopy (SEIRAS) analysis. The results show that the Pt electrode has high oxidation activity and significant poison behavior; on the contrary, the Au electrode demonstrates low activity without a poison peak. The SEIRAS analyses reveal that both carbon monoxide (CO) and carbon dioxide (CO2) appear during anode sweeping, and the CO peak density decreases with increasing potential and finally is eliminated. During the cathodic scanning, the CO peak reappears, and the peak intensity increases with scanning cycles, demonstrating a high poison behavior and the C1 reaction route on Pt. On the Au electrode, CO2 and CO peaks were not observed; instead, an acetic acid peak appeared, indicating a C2 reaction path. For the Pt/Au composited electrodes, the electrochemical activities of the electrodes, as well as their poison behavior, increased with the deposition amount of Pt. However, the intensities of the poison peaks are smaller than those of oxidation ones; therefore, a higher tolerance to the CO poison can be achieved. For the 2 m-Pt/Au composite electrode, the activity is close to that of pure Pt, but the poison tolerance is 3 times the value of Pt. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：A new near-infrared (NIR) probe based on a coumarinyl ligand (CL) was designed and synthesized. The probe CL can be used for simultaneous fluorescent turn-on and colorimetric detection of Hg2+ and Ag+ in ethanol/water medium. Colorless solution of probe CL changed to light yellow or dark yellow after addition of Hg2+ or Ag+ ions. Meanwhile the maximum absorption band shifted from 379 nm to 404 nm and the intensity increased enormously (for Hg2+) or moderately (for Ag+). Probe CL displayed an extraordinarily large Stokes shift of 316 nm and addition of Hg2+ or Ag+ to probe CL induced enhancement in the intensity of fluorescence emission at 695 nm by 15 or 8 fold. The detection limit of CL for Hg2+ and Ag+ ions is 0.83 and 8.8 lM, respectively. The applicable pH for sensing Hg2+ by probe CL is in a broad range of 2-12. Application of probe CL for in vitro U87MG cell imaging to detect Hg2+ ions was confirmed. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：Human telomerase RNA (hTR) is one essential component of telomerase and is overexpressed in tumor cells. Therefore, the reliable and sensitive detection of hTR is essential for the early cancer diagnosis. Herein, to avoid the false positive signals caused by co-existing components in the cell, a ratiometric fluorescence resonance energy transfer (FRET) strategy was developed to achieve reliable detection of intracellular hTR. Manganese dioxide nanosheets (MnO2NS) with good biocompatibility carry two fluorophore-labelled hairpin DNA probes into the cancer cell and then release the probes via decomposition of MnO2NS by intracellular L-glutathione reduced (GSH). Then, hTR triggered the cyclic strand displacement reaction (SDR) between two hairpin DNA probes to continuously form DNA duplexes, which made two fluorophores close to each other and led to an effective FRET. Fluorescence imaging demonstrated a higher expression level of hTR in HeLa cells than that in normal HL-7702 cells. The high specificity of hairpin DNA probes and SDR make it easy to discriminate the single-base mutation. Therefore, it provides a highly sensitive, simple and reliable method for the extracellular and intracellular detection of hTR. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：Both HClO and pH are essential players in multiple biological processes, which thus need to be controlled properly. Dysregulated HClO or pH correlates with many diseases. To meet these challenges, we need to develop highly competent probes for monitoring them. Over the years, despite a rich history of the development of HClO or pH probes, those that can do both jobs are still deficient. Herein, we present a novel dual-functional chemosensor, CMHN, which exhibits a blue and red shift of its fluorescence emission upon reacting with HClO or OH-, respectively. CMHN was successfully harnessed in the imaging detection of HClO or OH- in aqueous solutions, live cells, and zebrafish. Results indicated CMHN can detect HClO with high sensitivity (LOD -132 nM), a quick response time (<70 s), and high selectivity over dozens of interfering species through a colorimetric and ratiometric response. Besides, CMHN can probe pH changes sensitively and reversibly. Its working mechanism was verified by DFT calculations. These superior features make CMHN excel among the HClO or pH probes reported so far. Taken together, CMHN replenishes the deficiency in currently developed HClO or pH probes and paves the way for developing multifunctional HClO or pH probes in the future. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：A double signal amplification method was developed for sensitive detection of Hg2+ based on exonuclease III (Exo III) and Polymerase Chain Reaction (PCR). In the presence of Hg2+, the ineffective primers could bind with helper DNA to form dsDNA by T-Hg(II)-T mismatch for the first signal amplification. Then, the ineffective primers were digested by Exo III to effective primers which initiate PCR reaction for the second signal amplification. This conversion from ineffective to effective primers for triggering PCR reaction has not been reported for the detection of Hg2+. Through the double signal amplification strategy, the sensitivity of this proposed method was significantly improved with the limit of detection 1.46 nM. With the specific T-Hg(II)-T recognition, the selectivity of this new method was satisfactory. And the recoveries were between 92.3 % and 109.0 %. These results suggested that the proposed method was reliable to detect Hg2+ in water samples. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：Detection of copper plays a prominent role in the environmental protection and human health. Herein, we firstly design and construct an "off-on" upconversion fluorescence resonance energy transfer (UFRET) probe with low toxicity for the Cu2+ determination by using NaYF4: Yb3+, Er3+ upconversion nanoparticles (UCNPs) and Au NPs. UCNPs with positive charge and Au NPs with negative charge are respectively employed as the donor and acceptor, and bound together to form UFRET probe. The upconversion fluorescence quenching of UCNPs occurs by Au NPs through FRET (defined as "off" state). When Cu2+ exists in samples, Cu2+ reacts with 4-mercaptobenzoic acid (4-MBA) capped on the surface of Au NPs to make Au NPs detach from UCNPs, leading to the termination of FRET and the recovery of upconversion fluorescence (defined as "on" state). "Off-on" typed UFRET probe has excellent sensing performances, including linear range of 0.02-1 mu M Cu2+ concentration, the limit of detection of 18.2 nM, high selectivity to Cu2+ and good recovery. The probe has been successfully used to determine Cu2+ in spiked tap water with satisfactory results. The probe will provide theoretical and technical support for the design of new sensitive heavy metal ion detection probe. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：Two fluorescent D-A-D styryl-benzothiadiazole fluorophores possessing either styryl-BTD-styryl (2) or aryl-BTD-styryl (4) architectures have been synthesized using Heck reactions as key step. Compounds presented absorption in blue region and emission ranging from 531 to 560 nm with positive solvatochromism. Lippert Mattaga plots indicated a substantial effect of solvent polarity over the emission profile. As the fluorescence of the compound 4 was more sensitive to changes in the environment, this compound was evaluated as a probe to chemosensing etanol/water percentage in hydroalcoholic solutions. Good linearity was observed between fluorescence intensity and ethanol content in the range from 40% to 90%. Analyses of commercial solutions of sanitizers and cleaning products (%(ethanol) = 46%, 70% and 92%) indicate that reference values are within the confidence interval of experimental results produced by the proposed method. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：In this work, a novel signal amplification biosensor was utilized to detect Cd2+ based on asymmetric PCR. In the presence of Cd2+, it can bind with Cd2+-aptamer C1 which caused the complementary strand C2 to be released from double-stranded DNA C1-C2. Because the single-stranded C1 cannot be hydrolyzed by Exo III, it can be used as a template to take part in asymmetric PCR reaction. In the absence of Cd2+, the C1-C2 was digested by Exo III and no PCR template was left. During the experiment, an interesting phenomenon was found that the asymmetric PCR can obtain higher level of fluorescent signal than that of symmetric PCR. To the best of our knowledge, this is the first report of using asymmetric PCR to detect Cd2+. Through the asymmetric PCR amplification strategy, this biosensor had a low detection limit (19.93 nM) and a wide linear range (0-500 nM). Meanwhile, this biosensor showed a satisfactory selectivity and recovery rate. (C) 2022 Elsevier B.V. All rights reserved.
查看更多>>摘要：A rhodamine-based compound (RBO), which has been constructed from the reaction between N-(rhoda mine-6G)lactam-ethylenediamine and 2,1,3-benzoxadiazole-4-carbaldehyde, is reported here as a selective chemosensor for both Al3+ and Hg2+ ions in 10 mM HEPES buffer in water:ethanol (1:9, pH = 7.4). Absorption intensity of RBO increases considerably at 528 nm with these cations. It shows fluorescence enhancement at 550 nm by 1140- and 524-fold in the presence of Al3+ and Hg2+, respectively. LOD has been determined as 6.54 and 16.0 nM for Al3+ and Hg2+, respectively. Quantum yield and lifetime of RBO enhances with these metal ions. Fluorescence intensity of Al-probe complex or Hg-probe complex is quenched in the presence of fluoride or sulfide ion, respectively, opening a path for the construction logic gates. DFT analysis has been used to understand the spectral transitions. We have constructed a systematic development from single to five inputs complex circuit, and for the first time a time dependent five input complex logic circuit is reported herein. (C) 2022 Elsevier B.V. All rights reserved.
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