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1.
Proc Natl Acad Sci U S A ; 119(40): e2200835119, 2022 10 04.
Artigo em Inglês | MEDLINE | ID: mdl-36161936

RESUMO

Ice cores from alpine glaciers are unique archives of past global and regional climate conditions. However, recovering climate records from these ice cores is often hindered by the lack of a reliable chronology, especially in the age range of 100 to 500 anni (a) for which radiometric dating has not been available so far. We report on radiometric 39Ar dating of an ice core from the Tibetan Plateau and the construction of a chronology covering the past 1,300 a using the obtained 39Ar ages. This is made possible by advances in the analysis of 39Ar using the laser-based detection method atom trap trace analysis, resulting in a twofold increase in the upper age limit of 39Ar dating. By measuring the anthropogenic 85Kr along with 39Ar we quantify and correct modern air contamination, thus removing a major systematic uncertainty of 39Ar dating. Moreover, the 85Kr data for the top part of the ice core provide information on firn processes, including the age difference between the ice and its enclosed gas. This first application of 39Ar and 85Kr to an ice core facilitates further ice cores from nonpolar glaciers to be used for recovering climate records of the Common Era, a period including pronounced anomalies such as the Little Ice Age and the Medieval Warm Period.


Assuntos
Camada de Gelo , Datação Radiométrica , Clima , Mudança Climática , Datação Radiométrica/métodos , Tibet
2.
Anal Chem ; 96(4): 1427-1435, 2024 01 30.
Artigo em Inglês | MEDLINE | ID: mdl-38226591

RESUMO

Although porphyrins make up a promising class of electrochemiluminescence (ECL) luminophors, their aggregation-caused quenching (ACQ) characteristics lead to inferior ECL efficiency (ΦECL). Furthermore, current application of porphyrins is limited to cathodic emission. This work creatively exploited a cage-like porous complex (referred to as SWU-1) as the microreactor to recede the ACQ effect while modulating dual ECL emission of meso-tetra(4-carboxyphenyl)porphine (TCPP), which self-assembled with SWU-1 to form TCPP@SWU-1 nanocapsules (TCPP@SWU-1 NCs). As the microreactor, SWU-1 not only effectively constrained TCPP aggregation to improve electron-hole recombination efficiency but also improved stability of anion and cation radicals, thus significantly enhancing the dual emission of TCPP. Compared with TCPP aggregates, the resulting TCPP@SWU-1 NCs exhibited significantly enhanced anodic and cathodic emission, and their ΦECL was increased by 8.7-fold and 3.9-fold, respectively. Furthermore, black hole quencher-2 (BHQ2) can simultaneously quench anodic and cathodic signals. TCPP@SWU-1 NCs coupling BHQ2 conveniently achieved an ECL ratio detection of miRNA-126, and the limit of detection (S/N = 3) was 4.1 aM. This work pioneered the development of the cage-like porous complex SWU-1 as the microreactor to alleviate defects of the ACQ effect and mediate dual emission of TCPP. The coupling of dual-emitting TCPP@SWU-1 NCs and dual-function moderator BHQ2 created a novel single-luminophor-based ratio system for bioanalysis and provided a promising ECL analysis approach for miRNA-126.


Assuntos
Técnicas Biossensoriais , MicroRNAs , Porfirinas , Porosidade , Fotometria , Medições Luminescentes/métodos , Técnicas Eletroquímicas/métodos
3.
Opt Express ; 32(8): 13851-13863, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38859344

RESUMO

This paper introduces an innovative, compact, and high-gain metasurface antenna, covering both the 24 GHz millimeter wave (mmWave) radar band and the 5 G n257 and n258 bands. The proposed metasurface antenna consists of a wideband stacked patch antenna and a dual-layer metasurface to focus its radiation beams for multiple mmWave bands. The operating frequency can be slightly shifted by altering the distance between the feeder and the metasurface. The distribution of the metasurface unit cells is designed based on a simplified phase compensation formula. The dimension of the fabricated feeder is 6 mm × 6 mm, and the metasurface occupies a 65 mm × 65 mm radome area. Experimental results demonstrate a wide bandwidth from 23.5 GHz to 29.1 GHz for the feeder, and impressive maximum gains of 19.7 dBi and 19.5 dBi for the lower band and higher band of the metasurface antenna are achieved simultaneously. The frequency reconfiguration ability was characterized by a 750 MHz frequency shift with every 1 mm distance adjustment. The compact size and high gain performance of the proposed design underscore its potential for practical applications in millimeter wave joint communication and radar sensing systems.

4.
Anal Chem ; 95(49): 18207-18214, 2023 12 12.
Artigo em Inglês | MEDLINE | ID: mdl-38010370

RESUMO

Owing to excellent catalytic activity, single-atom catalysts (SACs) have recently attracted considerable research interest in the electrochemiluminescence (ECL) field. However, the applications of SACs are mostly limited to conventional luminol ECL system. Hence, it is necessary to explore the application of SACs in more ECL systems. In this work, nickel single-atom catalysts (Ni SACs) were successfully applied in the graphitic carbon nitride (g-C3N4)-H2O2 ECL system to significantly enhance its cathodic emission. Notably, g-C3N4 acted not only as an ECL luminophore but also as a support to anchor Ni SACs. Ni SACs can significantly activate H2O2 to produce abundant OH• radicals for enhancing the cathodic ECL emission of g-C3N4. Ni SACs-anchored g-C3N4 (Ni SACs@g-C3N4) had a 10-fold enhanced ECL intensity as compared to g-C3N4. Finally, the Ni SACs@g-C3N4-H2O2 ECL system was developed to detect hepatitis B virus (HBV) DNA by incorporating an entropy-driven DNA walking machine-assisted CRISPR-Cas12a amplification strategy. The constructed biosensor exhibited excellent detection performance for HBV DNA with a limit of detection as low as 17 aM. This work puts forward a new idea for enhancing the cathodic ECL of g-C3N4-H2O2 and expands the application of SACs in the ECL system.


Assuntos
Técnicas Biossensoriais , DNA Viral , Níquel , Técnicas Eletroquímicas , Peróxido de Hidrogênio , Medições Luminescentes , Limite de Detecção
5.
Anal Chem ; 94(23): 8346-8353, 2022 06 14.
Artigo em Inglês | MEDLINE | ID: mdl-35639506

RESUMO

Currently reported polyfluorene-based fluorescence detection usually shows high background signal and low detection sensitivity. This work developed a novel three-dimensional (3D) DNA rolling walker via directional movement on a lipid bilayer (LB) supported by Au@Fe3O4 nanoparticles (NPs) in a polyfluorene-based fluorescence system so that it could achieve significantly improved detection sensitivity and almost zero-background signal detection for miRNA-16. First, the carboxyl-functionalized poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadazole)] polymer nanoparticles (c-PFBT PNPs) covalently bonded with amino-labeled single-strand CP and further hybridized with single-strand AP to prepare AP-CP-coupled c-PFBT PNP probes. Meanwhile, Au@Fe3O4 NPs were developed as efficient fluorescence quenchers and served as the matrix for assembling the LB. The resulting Au@Fe3O4@LB assembled cholesterol-labeled orbital DNA L1 and L2 and further assembled hairpins H1 and AP-CP-coupled c-PFBT PNP probes to construct DNA nanomachines. Then, the target miRNA-16 was introduced to initiate the rolling circle amplification (RCA) reaction and form dynamic DNA rolling walkers, thus releasing single-strand CP-coupled c-PFBT PNP probes. The magnetic separation effect of Au@Fe3O4 NPs made it possible to detect the fluorescence signal from the released probes, thus achieving almost zero-background signal detection for miRNA-16 with a low detection limit of 95 aM. The flexible interfaces provided by the LB endowed the DNA rolling walkers with high binding efficiency and low derailment probability, thus achieving significantly improved detection sensitivity. The developed strategy provided an attractive polyfluorene-based fluorescence platform with high-sensitivity and low-background signals.


Assuntos
Técnicas Biossensoriais , MicroRNAs , Nanopartículas , Técnicas Biossensoriais/métodos , DNA , Limite de Detecção , Bicamadas Lipídicas , Técnicas de Amplificação de Ácido Nucleico/métodos , Andadores
6.
Mov Disord ; 37(7): 1531-1535, 2022 07.
Artigo em Inglês | MEDLINE | ID: mdl-35507442

RESUMO

BACKGROUND: Wilson's disease (WD) currently lacks a promising indicator that could reflect neurological impairment and monitor treatment outcome. We aimed to investigate whether serum neurofilament light chain (sNfL) functions as a candidate for disease assessment and treatment monitoring of WD. METHODS: We assessed preclinical and manifested WD patients' sNfL levels compared to controls and analyzed the differences between patients with various clinical symptoms. We then explored the correlation between clinical scales and sNfL levels. And repeated measurements were performed in 34 patients before and after treatment. RESULTS: WD patients with neurological involvement had significantly higher sNfL levels than both hepatic patients and controls. Positive correlations were found between Unified Wilson's Disease Rating Scale scores and sNfL and between semiquantitative magnetic resonance imaging scales and sNfL levels in WD patients. However, in the treatment follow-up analysis, the trend of sNfL before and after treatment disaccorded with clinical response. CONCLUSION: These findings suggest that sNfL levels can be an ideal indicator for the severity of neurological involvement but fail to evaluate change in disease condition after treatment. © 2022 International Parkinson and Movement Disorder Society.


Assuntos
Degeneração Hepatolenticular , Biomarcadores , Degeneração Hepatolenticular/diagnóstico , Degeneração Hepatolenticular/terapia , Humanos , Filamentos Intermediários , Imageamento por Ressonância Magnética , Resultado do Tratamento
7.
Clin Gastroenterol Hepatol ; 19(3): 590-596, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-32485301

RESUMO

BACKGROUND & AIMS: Wilson disease is an autosomal recessive disorder that impairs copper homeostasis and is caused by homozygous or compound heterozygous mutations in ATP7B, which encodes a copper-transporting P-type ATPase. Patients have variable clinical manifestations and laboratory test results, resulting in diagnostic dilemmas. We aimed to identify factors associated with symptoms and features of Wilson disease from a large cohort, over 15 years. METHODS: We collected data from 715 patients (529 with symptoms, 146 without symptoms, and 40 uncategorized) and a genetic confirmation of Wilson's disease (mean age of diagnosis, 18.84 years), recruited from 3 hospitals in China from 2004 through 2019. We analyzed clinical data along with serum levels of ceruloplasmin (available from 636 patients), 24-hr urinary copper excretion (collected from 131 patients), Kayser-Fleisher rings (copper accumulation in eyes, with neurologic data from 355 patients), and magnetic resonance imaging (MRI) abnormalities. Differences among the groups were analyzed using 1-way analysis of variance followed by Tukey multiple comparison test. RESULTS: Of the 529 patients with symptoms, 121 had hepatic features, 355 had neurologic features, 28 had osteomuscular features (premature osteoarthritis, skeletal deformities, and pathological bone fractures), and 25 had psychiatric symptoms. Age of onset was significantly younger in patients with hepatic (16.94 ± 1.03 years; P = .0105) or osteomuscular features (13 ± 1.33 years; P = .0001) than patients with neurological features (19.48 ± 0.46 years). Serum levels of ceruloplasmin differed among asymptomatic patients and patients with osteomuscular or neurologic symptoms of Wilson disease. Serum levels of ceruloplasmin ranged from 18.93 mg/L to approximately 120.00 mg/L (quantiles of 0.025 to approximately 0.975). Fifty-one of 131 patients (39%) had urinary copper excretion levels below 100 µg/24 hr; there was significant variation in levels of urinary copper excretion between patients older than 14 years vs 14 years or younger. Of the 355 patients with neurologic features, 244 patients (69%) had abnormal findings from MRI and Kayser-Fleisher rings; only 1 patient with abnormal findings from brain MRI was negative for Kayser-Fleisher rings. CONCLUSIONS: Serum level of ceruloplasmin, 24-hour urinary copper excretion, and Kayser-Fleisher rings can be used to identify patients who might have Wilson disease. Patients with serum levels of ceruloplasmin below 120 mg/L and children with urinary copper excretion above 40 µg should undergo genetic testing for Wilson's disease. Patients with movement disorders and brain MRI abnormalities without Kayser-Fleisher rings are not likely to have Wilson disease.


Assuntos
Degeneração Hepatolenticular , Adolescente , Ceruloplasmina/metabolismo , Criança , Cobre/metabolismo , Testes Genéticos , Degeneração Hepatolenticular/diagnóstico , Degeneração Hepatolenticular/genética , Humanos
8.
Anal Chem ; 2021 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-34133127

RESUMO

The bifunctional moderator is urgently needed in the field of ratiometric electrochemiluminescence (ECL) sensing since it can mediate simultaneously two ECL signals to conveniently realize their opposite change trend. This work designed a novel dual-signal combined nanoprobe with carboxyl-functionalized poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadazole)] nanoparticles (c-PFBT NPs) as the anodic ECL probe and L-cysteine capped CdS quantum dots (L-CdS QDs) as the cathodic ECL probe, which performed a dual-signal output capability without any additional coreactants. More importantly, hydrogen peroxide (H2O2) produced in situ by enzyme-catalyzed reaction was developed as a bifunctional moderator for simultaneously regulating two signals. The dual-signal combined nanoprobe (c-PFBT NPs@CdS QDs) served as the matrix to immobilize acetylcholinesterase (AChE) and choline oxidase for organophosphorus (OPs) analysis. In the absence of OPs, H2O2 was produced by catalyzing the substrate acetylthiocholine (ATCl) with enzymes and it quenched the anodic ECL signal from c-PFBT NPs and simultaneously promoted the cathodic ECL signal from L-CdS QDs. When OPs was present, the activity of AChE was inhibited, the anodic signal would increase, and the cathodic signal would accordingly decrease. The integration of the bifunctional moderator H2O2 and dual-signal combined nanoprobe c-PFBT NPs@CdS QDs not only provides an attractive ECL platform for enzymatic sensing involving the generation or consumption of H2O2 but also paves a new pathway for other ratiometric ECL systems involving enzyme catalytic amplification for detecting antigens, antibodies, DNA, RNA, etc.

9.
Opt Express ; 29(19): 30579-30589, 2021 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-34614780

RESUMO

This paper presents a new design of linear-polarization metasurface converter with arbitrary polarization rotating angle. The linear-polarization conversion is achieved by first separating the linearly polarized incident wave into two orthogonal circularly polarized waves, then adding an additional phase to one of the circularly polarized waves, and finally recombining these two circularly polarized waves into a linearly polarized wave and reflecting it towards free space. A practical unit cell operating at 10 GHz with sandwich structure is applied to realize the linear-polarization metasurface converter, which consists of a top-layer square patch, a middle-layer ground plane, a bottom-layer 90° quadrature hybrid coupler, and two vias connecting the top layer and bottom layer. The proposed linear-polarization metasurface converter is analyzed theoretically and demonstrated by both simulating and experimental results.

10.
Opt Express ; 29(20): 32031-32041, 2021 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-34615282

RESUMO

We present a time-coding reconfigurable intelligent surface (RIS) enabled spread-spectrum secure wireless communication system. The time-coding spread-spectrum RIS is realized by altering the RIS between the two states of a perfect electrical conductor (PEC) and perfect magnetic conductor (PMC), according to a pseudo-random time sequence, respectively. This spectrum spreading function of the time-coding RIS can be simply applied to the secure wireless communication systems, providing a low-cost, easy-implementation encrypting architecture with the two key features of interception prevention and interference suppression. These two features together with the overall spread-spectrum secure wireless communication system are demonstrated by both theoretical analysis and experimental results using a designed 8 × 8 time-coding RIS.

11.
Opt Express ; 29(2): 2658-2668, 2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-33726457

RESUMO

Programmable reflective metasurfaces that combine the features of reconfigurable phased array antennas and reflectors are an effective solution for radar and modern communication systems. However, most of the demonstrated active metasurfaces support tunable responses for a specific frequency band. Thus, we propose a programmable metasurface that combines the advantages of multi-bit phase quantization and dual-band operations. To actively control the diverse functions, two PIN diodes are integrated on the radiating element, and these diodes are controlled by the biasing voltage. The unit cell is fabricated, and experimental characterization is performed in the waveguide measurement setup. The proposed design can be applied for imaging and high-capacity wireless communications.

12.
Opt Express ; 29(2): 1470-1480, 2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-33726361

RESUMO

This paper proposes an electronically reconfigurable unit cell for transmit-reflect-arrays in the X-band, which makes it possible to control the reflection or transmission phase independently by combining the mechanisms of reconfigurable transmitarrays and reconfigurable reflectarrays. The fabricated unit cell was characterized in a waveguide simulator. The return loss in the reflection mode and insertion loss in the transmission mode are smaller than 1.8 dB for all states at 10.63 GHz, and a 1-bit phase shift for both modes is achieved within 180° ± 10°. When compared to full-wave electromagnetic simulation results, the proposed unit cell shows good results and is thus verified.

13.
Opt Express ; 28(2): 1139-1149, 2020 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-32121829

RESUMO

In this paper, a multi-bit dielectric reflective metasurface is presented for control of electromagnetic (EM) wave scattering and anomalous reflection. The unit cell is designed to act as a 1-, 2-, and 3-bit coding metasurface to attain better control of EM waves. For the 3-bit coding metasurface, the eight digital states have phase responses of 0°, 45°, 90°, 135°, 180°, 225°, 270°, and 315°. The top layer of the proposed metasurface consists of high permittivity material to realize a high Q factor. The proposed multi-bit coding metasurface can reflect the incident EM wave to the desired angle with more than 93% power efficiency. For radar cross section reduction applications, the discrete water cycle algorithm is utilized to obtain an optimal coding matrix for the unit cell arrangement, leading to better diffusion-like scattering, dispersion of the EM wave in all directions, and hence minimal specular reflection. The simulation and experimental results verify that the proposed metasurface is a suitable candidate for control of EM wave scattering and anomalous reflection.

14.
Anal Chem ; 91(21): 13576-13581, 2019 11 05.
Artigo em Inglês | MEDLINE | ID: mdl-31550899

RESUMO

The noble gas radioisotopes 85Kr, 81Kr, and 39Ar are nearly ideal environmental tracers because of their chemical inertness and simple transport mechanisms. Recent advances in Atom Trap Trace Analysis have enabled measurements of 85Kr and 81Kr using 10-20 kg of water or ice, and 39Ar in only a few kilograms, making these tracers available to be applied in the earth sciences on a large-scale. To meet the resulting increase in demand, we have developed an automated process for the dual separation of krypton and argon from environmental samples based on titanium gettering and gas chromatography. 0.5-4 L STP air samples have been purified, demonstrating purities and recoveries of >90% for krypton and >99% for argon within 90-120 min of processing time. Samples of high methane admixtures, a challenge regularly encountered in groundwater applications, have been purified by exploiting the full potential of titanium gettering at high temperatures (>1000 °C). Samples with 0.4-48 L STP of methane admixture are processed in 2-5 h without compromising purity or recovery. The applicability of the purification system is further demonstrated using actual groundwater samples with carbon dioxide and methane content in the extracted gas up to 16 L STP and 42 L STP, respectively.

15.
Opt Express ; 27(24): 34864-34875, 2019 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-31878666

RESUMO

Orbital angular momentum (OAM) beam generators have attracted tremendous interests recently due to their excellent performance and potential applications in wireless communication. However, the existing transmissive OAM generators suffer from several limitations, such as narrow bandwidth, high profile and low efficiency. In this study, a new wideband third-order meta-frequency selective surface (meta-FSS) for generating focusing vortex beam is developed. The proposed meta-FSS element is designed at X- band with a third-order band-pass filter property, which exhibits the merits of low profile, high transmissivity, and large angular stability. By employing the proposed meta-FSS element, prototypes of OAM generators for + 1 and -2 modes are designed, fabricated, and measured. Experimental results verify the ability of the proposed design to convert an incident left/right-handed circularly polarized (L/RHCP) spherical wave into a transmitted R/LHCP vortex carrying OAM wave from 9.0 GHz to 11.0 GHz with high mode purity. A good agreement is achieved between the experimental and numerical results, which demonstrates that the proposed structure paves the wave for generating desired OAM modes, and provides new possibility for designing novel low-profile wireless communication devices.

16.
J Chem Phys ; 147(8): 084705, 2017 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-28863548

RESUMO

During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and about eight water molecules in the first hydration shell within a radius of 3.3 Å at all higher hydration states. Moreover, the MD results show that the complete hydration shells are nearly spherical with an orthogonal coordination sphere. They could only be formed when the basal spacing d001 ≥ 18.7 Å, i.e., approximately, the interlayer separation h ≥ 10 Å. Comparison between DFT and MD simulations shows that DFT failed to reproduce the outer-sphere complexes in the Stern-layer (within ∼5.0 Å from the clay basal-plane), observed in the MD simulations.

17.
Sensors (Basel) ; 17(1)2016 Dec 29.
Artigo em Inglês | MEDLINE | ID: mdl-28036085

RESUMO

RFID ownership transfer protocols (OTPs) transfer tag ownership rights. Recently, there has been considerable interest in such protocols; however, guaranteeing privacy for symmetric-key settings without trusted third parties (TTPs) is a challenge still unresolved. In this paper, we address this issue and show that it can be solved by using channels with positive secrecy capacity. We implement these channels with noisy tags and provide practical values, thus proving that perfect secrecy is theoretically possible. We then define a communication model that captures spatiotemporal events and describe a first example of symmetric-key based OTP that: (i) is formally secure in the proposed communication model and (ii) achieves privacy with a noisy tag wiretap channel without TTPs.

18.
J Chem Phys ; 142(19): 194110, 2015 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-26001450

RESUMO

Based on the best available knowledge of density functional theory (DFT), the reference-fluid perturbation method is here extended to yield different approaches that well account for the cross correlations between the Columbic interaction and the hard-sphere exclusion in an inhomogeneous ionic hard-sphere fluid. In order to quantitatively evaluate the advantage and disadvantage of different approaches in describing the interfacial properties of electrical double layers, this study makes a systematic comparison against Monte Carlo simulations over a wide range of conditions. The results suggest that the accuracy of the DFT approaches is well correlated to a coupling parameter that describes the coupling strength of electrical double layers by accounting for the steric effect and that can be used to classify the systems into two regimes. In the weak-coupling regime, the approaches based on the bulk-fluid perturbation method are shown to be more accurate than the counterparts based on the reference-fluid perturbation method, whereas they exhibit the opposite behavior in the strong-coupling regime. More importantly, the analysis indicates that, with a suitable choice of the reference fluid, the weighted correlation approximation (WCA) to DFT gives the best account of the coupling effect of the electrostatic-excluded volume correlations. As a result, a piecewise WCA approach can be developed that is robust enough to describe the structural and thermodynamic properties of electrical double layers over both weak- and strong-coupling regimes.

19.
Anal Chem ; 86(8): 4002-7, 2014 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-24641193

RESUMO

Long-lived radioactive krypton isotopes, (81)Kr (t1/2 = 229,000 year) and (85)Kr (t1/2 = 10.76 year), are ideal tracers. (81)Kr is cosmogenic and can be used for dating groundwater beyond the (14)C age. (85)Kr is a fission product and can be applied in atmospheric studies, nuclear safety inspections, and dating young groundwater. It has long been a challenge to analyze radio-krypton in small samples, in which the total number of such isotopes can be as low as 1 × 10(5). This work presents a system developed to analyze (81)Kr and (85)Kr from a few liters of air samples. A separation system based on cryogenic distillation and gas chromatographic separation is used to extract krypton gas with an efficiency of over 90% from air samples of 1-50 L. (85)Kr/Kr and (81)Kr/Kr ratios in krypton gases are determined from single-atom counting using a laser-based atom trap. In order to test the performance of the system, we have analyzed various samples collected from ambient air and extracted from groundwater, with a minimum size of 1 L. The system can be applied to analyze (81)Kr and (85)Kr in environmental samples including air, groundwater, and ices.

20.
Biosens Bioelectron ; 237: 115539, 2023 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-37487285

RESUMO

Constructing mono-luminophor-based electrochemiluminescence (ECL) ratio system is a great challenge due to the limitations of the luminescent species with dual-signal-output, luminescence efficiency and coreactant. This work developed carboxyl-functionalized poly[9,9-bis(3'-(N,N-dimethylamino) propyl)-2,7-fluorene]-alt-2,7-(9,9 dioctylfluorene)] nanoparticles(PFN NPs) as dual-emitting luminophors, which can synchronously output strong cathodic and anodic ECL signals without any exogenous coreactants. The inherent molecular structure enabled efficient intramolecular electron transfer between tertiary amine groups and backbone of PFN to generate strong cathodic and anodic ECL emission. Particularly, H+ in aqueous solution played an irreplaceable role for cathodic ECL emission. The silver nanoparticles (AgNPs) were developed as signal regulator because of their excellent hydrogen evolution reaction (HER) activity, which significantly quenched the cathodic signal while kept the anodic signal unchanged. The dual-emitting PFN NPs cleverly integrated signal regulator AgNPs and bicyclic strand displacement amplification (SDA) to construct a coreactant-free mono-luminophor-based ratiometric ECL sensing for SARS-CoV-2 RdRp gene assay. The strong dual-emitting of PFN NPs and excellent quenching effect of AgNPs on cathodic emission endowed the biosensor with a high detection sensitivity, and the detection limit was as low as 39 aM for RdRp gene. The unique dual-emitting properties of PFN NPs open up a new path to construct coreactant-free mono-luminophor-based ECL ratio platform, and excellent HER activity of AgNPs offers some new thoughts for realizing ECL signal changes.


Assuntos
Técnicas Biossensoriais , COVID-19 , Nanopartículas Metálicas , Humanos , Polímeros/química , Nanopartículas Metálicas/química , SARS-CoV-2/genética , Medições Luminescentes , COVID-19/diagnóstico , Prata , RNA Polimerase Dependente de RNA , Técnicas Eletroquímicas
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