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Single-atom nanozyme-based catalytic therapy is of great interest in the field of tumor catalytic therapy; however, their development suffers from the low affinity of nanozymes to the substrates (H2O2 or O2), leading to deficient catalytic activity in the tumor microenvironment. Herein, we report a new strategy for precisely tuning the d-band center of dual-atomic sites to enhance the affinity of metal atomic sites and substrates on a class of edge-rich N-doped porous carbon dual-atomic sites Fe-Mn (Fe1Mn1-NCe) for greatly boosting multiple-enzyme-like catalytic activities. The as-made Fe1Mn1-NCe achieved a much higher catalytic efficiency (Kcat/Km = 4.01 × 105 S-1·M-1) than Fe1-NCe (Kcat/Km = 2.41 × 104 S-1·M-1) with an outstanding stability of over 90% activity retention after 1 year, which is the best among the reported dual-atom nanozymes. Theoretical calculations reveal that the synergetic effect of Mn upshifts the d-band center of Fe from -1.113 to -0.564 eV and enhances the adsorption capacity for the substrate, thus accelerating the dissociation of H2O2 and weakening the O-O bond on O2. We further demonstrated that the superior enzyme-like catalytic activity of Fe1Mn1-NCe combined with photothermal therapy could effectively inhibit tumor growth in vivo, with an inhibition rate of up to 95.74%, which is the highest value among the dual-atom artificial enzyme therapies reported so far.
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Peróxido de Hidrogênio , Neoplasias , Humanos , Adsorção , Carbono , Catálise , Microambiente TumoralRESUMO
The volumetric density of the metal atomic site is decisive to the operating efficiency of the photosynthetic nanoreactor, yet its rational design and synthesis remain a grand challenge. Herein, we report a shell-regulating approach to enhance the volumetric density of Co atomic sites onto/into multishell ZnxCd1-xS for greatly improving CO2 photoreduction activity. We first establish a quantitative relation between the number of shell layers, specific surface areas, and volumetric density of atomic sites on multishell ZnxCd1-xS and conclude a positive relation between photosynthetic performance and the number of shell layers. The triple-shell ZnxCd1-xS-Co1 achieves the highest CO yield rate of 7629.7 µmol g-1 h-1, superior to those of the double-shell ZnxCd1-xS-Co1 (5882.2 µmol g-1 h-1) and single-shell ZnxCd1-xS-Co1 (4724.2 µmol g-1 h-1). Density functional theory calculations suggest that high-density Co atomic sites can promote the mobility of photogenerated electrons and enhance the adsorption of Co(bpy)32+ to increase CO2 activation (CO2 â CO2* â COOH* â CO* â CO) via the S-Co-bpy interaction, thereby enhancing the efficiency of photocatalytic CO2 reduction.
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Rapid and accurate detection of human epidermal growth factor receptor 2 (HER2) is crucial for the early diagnosis and prognosis of breast cancer. In this study, we reported an iron-manganese ion N-doped carbon single-atom catalyst (FeMn-NCetch/SAC) bimetallic peroxidase mimetic enzyme with abundant active sites etched by H2O2 and further demonstrated unique advantages of single-atom bimetallic nanozymes in generating hydroxyl radicals by density functional theory (DFT) calculations. As a proof of concept, a portable device-dependent electrochemical-photothermal bifunctional immunoassay detection platform was designed to achieve reliable detection of HER2. In the enzyme-linked reaction, H2O2 was generated by substrate catalysis via secondary antibody-labeled glucose oxidase (GOx), while FeMn-NCetch/SAC nanozymes catalyzed the decomposition of H2O2 to form OH*, which catalyzed the conversion of 3,3',5,5'-tetramethylbenzidine (TMB) to ox-TMB. The ox-TMB generation was converted from the colorimetric signals to electrical and photothermal signals by applied potential and laser irradiation, which could be employed for the quantitative detection of HER2. With the help of this bifunctional detection technology, HER2 was accurately detected in two ways: photothermally, with a linear scope of 0.01 to 2.0 ng mL-1 and a limit of detection (LOD) of 7.5 pg mL-1, and electrochemically, with a linear scope of 0.01 to 10 ng mL-1 at an LOD of 3.9 pg mL-1. By successfully avoiding environmental impacts, the bifunctional-based immunosensing strategy offers strong support for accurate clinical detection.
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Técnicas Eletroquímicas , Receptor ErbB-2 , Smartphone , Humanos , Imunoensaio/métodos , Receptor ErbB-2/análise , Receptor ErbB-2/imunologia , Peróxido de Hidrogênio/química , Peróxido de Hidrogênio/análise , Catálise , Limite de Detecção , Glucose Oxidase/química , Glucose Oxidase/metabolismo , Benzidinas/química , Manganês/química , Ferro/química , Neoplasias da Mama , Teoria da Densidade FuncionalRESUMO
Pursuing effective and generalized strategies for modulating the electronic structures of atomically dispersed nanozymes with remarkable catalytic performance is exceptionally attractive yet challenging. Herein, we developed a facile "formamide condensation and carbonization" strategy to fabricate a library of single-atom (M1-NC; 6 types) and dual-atom (M1/M2-NC; 13 types) metal-nitrogen-carbon nanozymes (M = Fe, Co, Ni, Mn, Ru, Cu) to reveal peroxidase- (POD-) like activities. The Fe1Co1-NC dual-atom nanozyme with Fe1-N4/Co1-N4 coordination displayed the highest POD-like activity. Density functional theory (DFT) calculations revealed that the Co atom site synergistically affects the d-band center position of the Fe atom site and served as the second reaction center, which contributes to better POD-like activity. Finally, Fe1Co1 NC was shown to be effective in inhibiting tumor growth both in vitro and in vivo, suggesting that diatomic synergy is an effective strategy for developing artificial nanozymes as novel nanocatalytic therapeutics.
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Peroxidase , Peroxidases , Carbono , Catálise , CorantesRESUMO
Cation exchange (CE) is a burgeoning method for controlled crystal synthesis; however, its applications in bioanalysis are still in their infancy. Herein, we explored the transformation of ZnIn2S4 in properties after the CE reaction with Cu2+ ions; furthermore, the discrepancy was employed to design a dual-readout detection system of photothermal and polarity-switchable photoelectrochemical (PEC) immunoassays to realize reliable detection of carcinoembryonic antigen (CEA). In the presence of CEA, the CuO nanoparticles (CuO NPs) employed as dual-signal response probes would bond to the microplates and be acidolyzed by HCl to release Cu2+, which could replace Zn2+ and In3+ via the CE reaction. After the CE reaction is completed, the photocurrent would switch from a weak anodic photocurrent to a cathode one by using a 635 nm laser as a signal amplifier, while the photothermal signal would be enhanced with 808 nm laser illumination. On the basis of the polarity-switchable PEC strategy, CEA could be accurately detected from 0.1 to 50 ng mL-1 with a limit of detection (LOD) of 48 pg mL-1 (S/N = 3). Moreover, the photothermal assay for CEA detection possesses a linear range from 0.5 to 100 ng mL-1 with a LOD of 0.21 ng mL-1. In addition, the designed sensing platform only relies on devices with portability that are permitted for point-of-care detection.
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Técnicas Biossensoriais , Antígeno Carcinoembrionário , Antígeno Carcinoembrionário/análise , Técnicas Eletroquímicas/métodos , Técnicas Biossensoriais/métodos , Imunoensaio/métodos , Limite de Detecção , CátionsRESUMO
The point-of-care (POC) method with affordability and portability for the sensitive detection of biological substances is an emerging topic in rapid disease screening and personalized medicine. In this work, we demonstrated a diverse responsive platform based on a dual-channel pressure sensor (DCPS). The DCPS had a multilayer flexible architecture consisting of a photonic hydrogel with chromatic transitions and a piezoresistive pressure sensor as the electrical data transmission unit, both of which had the property of pressure-induced mechanical stimulus feedback. By incorporating a platinum nanoparticles-labeled detection antibody (PtNPs-dAb) into the sandwich-type immunoreaction for the target carcinoembryonic antigen (CEA, as a model analyte), gas decomposition could be triggered by the addition of hydrogen peroxide (H2O2) to induce a significant increase under pressure in a closed chamber. Meanwhile, the DCPS enabled an accurate electrical signal output, and the photonic hydrogel converted spatiotemporal stimuli into eye-readable colorations with string brilliance. In this way, the target concentration could be quantificationally related to the electrical response and intuitively perceived through visible color alterations. Under optimal conditions, a sensitive determination of CEA was performed in a detectable range of 0.3-60 ng/mL with a limit of detection (LOD) of 0.13 ng/mL. In addition, the proposed protocol had satisfactory selectivity, accuracy, and reproducibility. Furthermore, an array-based immunoassay device was fabricated to conceptually validate its application potential in high-throughput biomedical detection and inspire a dual-signal POC diagnostic platform in a friendly way for resource-limited settings.
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Técnicas Biossensoriais , Nanopartículas Metálicas , Antígeno Carcinoembrionário , Ouro , Hidrogéis , Peróxido de Hidrogênio , Imunoensaio/métodos , Limite de Detecção , Platina , Sistemas Automatizados de Assistência Junto ao Leito , Reprodutibilidade dos TestesRESUMO
A magnetic-assisted photoelectrochemical (PEC) and colorimetric (CL) dual-modal biosensing platform with high precision was established to monitor prostate-specific antigen (PSA) based on Bi2MoO6 nanosheets (BMO) by coupling the aptamer-guided hybridization chain reaction (HCR) with the hydrolysate-induced vulcanization reaction of Bi2MoO6 nanosheets. Upon addition of PSA, trigger DNA (tDNA) was released by the interaction between the target analyte and the aptamer and then further hybridized with anchor DNA (aDNA) conjugated on magnetic beads (MBs). The as-released tDNA initiated the target-assisted HCR in the presence of two alternating hairpin sequences (Bio-H1 and Bio-H2) to produce nicked long double-stranded DNA on the surface of MBs, where numerous alkaline phosphatase (ALP) enzymes could assemble with MBs through the biotin-avidin reaction, resulting in the hydrolysis of sodium thiophosphate (TP) to H2S. The as-produced H2S reacted with BMO to form vulcanized BMO (BMO-S), thus leading to obvious enhanced PEC performance under visible light with the color change from light yellow to brown. Having optimized the test conditions, the magnetic-assisted biosensing system holds a good quantitative diagnosis sensitivity area in a range of 5.0 pg mL-1-100 ng mL-1 with a calculated detection limit down to 3.5 pg mL-1. Meanwhile, a visual colorimetric assay on basis of the change in the color of the materials was also realized. Given the exceptional performance of the constructed biosensor, it may possess great promise as an advanced bioanalytical tool for practical applications.
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Técnicas Biossensoriais , Antígeno Prostático Específico , Biocatálise , Bismuto , DNA , Técnicas Eletroquímicas/métodos , Humanos , Limite de Detecção , Masculino , MolibdênioRESUMO
This work reports a contactless photoelectrochemical biosensor based on an ultraviolet-assisted gas sensor (UV-AGS) with a homemade three-dimensional (3D)-SnS2 nanosheet-functionalized interdigitated electrode. After rigorous examination, it was found that the gas responsiveness accelerated and the sensitivity increased using the UV irradiation strategy. The effects of the interlayer structure and the Schottky heterojunction on the gas-sensitive response of O2 and NH3 under UV irradiation were further investigated theoretically by 3D electrostatic field simulations and first-principles density functional theory to reveal the mechanism. Finally, a UV-AGS device was developed to quantify the blood ammonia bioassay in a small-volume whole blood sample by alkalizing blood to release gas-phase ammonia with a linear range of 25-5000 µM with a limit of detection (LOD) of 29.5 µM. The device also enables a rapid immunoassay of human cardiac troponin I (cTnI) with a linear range of 0.4-25.6 ng/mL and an LOD of 0.37 ng/mL using a urease-labeled antibody as the immune recognition molecule. Both analyses showed satisfying specificity and stability, suggesting that the device can be applied to practical assays and is of great potential to increase the value of gas-sensitive sensors in chemical biosensing.
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Técnicas Biossensoriais , Técnicas Eletroquímicas , Amônia , Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Eletrodos , Humanos , Limite de DetecçãoRESUMO
Large-scale, rapid, and inexpensive serological diagnoses of severe acute respiratory syndrome-coronavirus-2 (SARS-CoV-2) are of great interest in reducing virus transmission at the population level; however, their development is greatly plagued by the lack of available point-of-care methods, leading to low detection efficiency. Herein, an ultrasensitive smartphone-based electrochemical immunoassay is reported for rapid (less than 5 min), low-cost, easy-to-implement detection of the SARS-CoV-2 nucleocapsid protein (SARS-CoV-2 N protein). Specifically, the electrochemical immunoassay was fabricated on a screen-printed carbon electrode coated with electrodeposited gold nanoparticles, followed by incubation of anti-N antibody (Ab) and bovine serum albumin as the working electrode. Accompanied by the antigen-antibody reaction between the SARS-CoV-2 N protein and the Ab, the electron transfer between the electroactive species [Fe(CN)6]3-/4- and the electrode surface is disturbed, resulting in reduced square-wave voltammetry currents at 0.075 V versus the Ag/AgCl reference electrode. The proposed immunoassay provided a good linear range with SARS-CoV-2 N protein concentrations within the scope of 0.01-1000 ng/mL (R2 = 0.9992) and the limit of detection down to 2.6 pg/mL. Moreover, the detection data are wirelessly transmitted to the interface of the smartphone, and the corresponding SARS-CoV-2 N protein concentration value is calculated and displayed. Therefore, the proposed portable detection mode offers great potential for self-differential diagnosis of residents, which will greatly facilitate the effective control and large-scale screening of virus transmission in resource-limited areas.
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Técnicas Biossensoriais , COVID-19 , Nanopartículas Metálicas , Humanos , SARS-CoV-2 , Ouro , Sistemas Automatizados de Assistência Junto ao Leito , Smartphone , COVID-19/diagnóstico , Imunoensaio/métodos , Técnicas Biossensoriais/métodosRESUMO
This work presented a point-of-care (POC) photoelectrochemical (PEC) biosensing for the detection of human papillomavirus-16 (HPV-16) on a portable electrochemical detection system by using CRISPR-Cas12a trans-cleaving the G-quadruplex for the biorecognition/amplification and a hollow In2O3-In2S3-modified screen-printed electrode (In2O3-In2S3/SPE) as the photoactive material. G-quadruplexes were capable of biocatalytic precipitation (H2O2-mediated 4-chloro-1-naphthol oxidation) on the In2O3-In2S3/SPE surface, resulting in a weakened photocurrent, but suffered from trans-cleavage when the CRISPR-Cas12a system specifically recognized the analyte. The photocurrent results could be directly observed with the card-sized electrochemical device via a smartphone, which displayed a high-value photocurrent for these positive samples, while a low-value photocurrent for the target-free samples. Such a system exhibited satisfying photocurrent responses toward HPV-16 within a wide working range from 5.0 to 5000 pM and allowed for detection of HPV-16 at a concentration as low as 1.2 pM. The proposed assay provided a smartphone signal readout to enable the rapid screening PEC determination of HPV-16 concentration without sophisticated instruments, thus meeting the requirements of remote areas and resource-limited settings. We envision that combining an efficient biometric PEC sensing platform with a wireless card-sized electrochemical device will enable high-throughput POC diagnostic analysis.
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Técnicas Biossensoriais , Ácidos Nucleicos , Técnicas Biossensoriais/métodos , Sistemas CRISPR-Cas , Técnicas Eletroquímicas , Humanos , Peróxido de Hidrogênio , Sistemas Automatizados de Assistência Junto ao LeitoRESUMO
Herein, we explore a general Cu2-x S nanocube template-assisted and reverse cation exchange-mediated growth strategy for fabricating hollow multinary metal sulfide. Unlike the traditional cation exchange method controlled by the metal sulfide constant, the introduction of tri-n-butylphosphine (TBP) can reverse cation exchange to give a series of hollow metal sulfides. A variety of hollow multinary metal sulfide cubic nanostructures has been demonstrated while preserving anisotropic shapes to the as-synthesized templates, including binary compounds (CdS, ZnS, Ag2 S, PbS, SnS), ternary compound (CuInS2 , Znx Cd1-x S), and quaternary compound (single-atom platinum anchored Znx Cd1-x S; Znx Cd1-x S-Pt1 ). Experimental and density functional theory (DFT) calculations show that the hollow metal sulfide semiconductors obtained could significantly improve the separation and migration of photogenerated electron-hole pairs. Owing to the efficient charge transfer, the Znx Cd1-x S-Pt1 exhibited outstanding photocatalytic performance of CO2 to CO, with the highest CO generation rate of 75.31â µmol h-1 .
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This work developed a near-infrared (near-IR) light-activated non-enzymatic signal-off photoelectrochemical (PEC) immunoassay for the ultrasensitive detection of α-fetoprotein (AFP) on the basis of branched polyethylenimine (BPEI)-modified upconversion nanoparticle (UCNP)@CdTe quantum dot (QD) nanostructures by coupling with the synergistic effect of dual-purpose copper ions. Emission light originated from NaYF4:Yb,Er UCNP was directly utilized through the electrostatic bonding of CdTe QDs to excite the separation of electron-hole pairs, resulting in the generation of obvious photocurrent under a 980 nm laser. By using polyclonal antibody-labeled cupric oxide nanoparticle as the secondary antibody, the nanolabel was introduced into the monoclonal anti-AFP antibody-modified microplates in the presence of target AFP. After treatment with acid, the as-released copper ion decreased the photocurrent through the synergistic effect with two issues: one was initially to form coordination with BPEI on the surface of UCNP, and then the near-IR excitation light and upconversion luminescence were attenuated due to the internal filter effect; another was to snatch the electrons flowing from the valence band of CdTe QD as the exciton trapping sites. Under optimal conditions, the dual-purpose Cu2+-activated signal-off PEC immunosensing platform exhibited a dynamic linear range from 10 pg mL-1 to 50 ng mL-1, accompanying the decreasing photocurrent with the increment of AFP concentration at an experimental detection limit of 1.2 pg mL-1. Importantly, good accuracy was achieved by this method in comparison with the results with human AFP ELISA kit for analysis of human serum samples. This dual-purpose Cu2+-activated PEC immunoassay brings a promising, enzyme-free and innovative thinking for the detection of low-abundance biomarkers.
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Cobre/química , Técnicas Eletroquímicas/métodos , Nanoestruturas/química , Processos Fotoquímicos , Polietilenoimina/química , Pontos Quânticos , alfa-Fetoproteínas/análise , Técnicas Biossensoriais , Compostos de Cádmio/química , Humanos , Imunoensaio , Limite de Detecção , Telúrio/químicaRESUMO
This work reports a strategy for glutathione-loaded liposome-encoded magnetic beads initiated by palindromic fragment-mediated single-chain amplification (PFMSCA) for high-precision quantification of a low-abundance aminoglycoside antibiotic (kanamycin; Kana) by using In2O3-ZnIn2S4 (IO-ZIS) as a photoactive matrix. In this strategy, a Kana-recognition region, primer-like palindromic fragment, and polymerization/nicking template are reasonably integrated into one oligonucleotide (hairpin HP1) for target recognition, magnetic separation, and target amplification. Upon target Kana introduction, the Kana-aptamer region in HP1 specifically recognizes the Kana and triggers the palindromic tails intramolecular self-hybridization, amplifying a large number of short fragments in the presence of Klenow fragment polymerase and Nt.BbvCI. The as-generated nick fragments act as a linker to introduce the free hairpin HP2-functionalized glutathione-loaded liposomes (HP2-GLL) onto the surface of the hairpin HP3-modified magnetic beads (HP3-MB), constructing liposome-encoded magnetic beads (HP3-MB-nick-HP2-GLL). Following magnetic separation, the detached glutathione-loaded liposomes (GLL) are lysed by treatment with 1% Triton X-100 to release the glutathione within it, which were then detected as an amplified photocurrent at the IO-ZIS-based photoelectrode. Importantly, this method can be readily carried out by using one oligonucleotide to achieve an exponential amplification effect and open new opportunities for advanced development of robust biodetection systems.
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Técnicas Biossensoriais/métodos , DNA de Cadeia Simples/química , DNA de Cadeia Simples/genética , Sequências Repetidas Invertidas , Processos Fotoquímicos , Eletroquímica , Glutationa/química , Limite de Detecção , Lipossomos/química , Imãs/química , Microesferas , Técnicas de Amplificação de Ácido NucleicoRESUMO
This work presented an innovative and rationally engineered palindromic molecular beacon (PMB) based "Z-scheme" photoelectrochemical (PEC) biosensing protocol for the selective screening of kanamycin (Kana) through DNA hybridization-induced conformational conversion. Interestingly, the ingeniously designed PMB integrated the multifunctional elements including recognition region, primer-like palindromic fragment, and polymerization-nicking template. The cosensitized structures consisted of CdS quantum dot functionalized hairpin DNA2 (QD-HP2) and region-selectively deposited gold nanoparticles onto {001} facets of bismuth oxychloride (BiOCl-Au). Compared with BiOCl-Au alone, the attachment of CdS QDs onto BiOCl-Au (i.e., BiOCl-Au-CdS QDs) exhibited evidently enhanced photocurrent intensity thanks to the synergistic effect of Z-scheme BiOCl-Au-CdS QDs. After incubation with target Kana, Kana-aptamer binding could induce the exposure of PMB region for hairpin DNA1 (HP1). The exposed palindromic tails hybridized with each other (like a molecular machine) to consume the substrates (dNTPs) and fuels (enzyme) for the releasing of numerous nick fragments (Nick). The as-generated nick fragments could specifically hybridize with the complementary region of QD-HP2, thus resulting in decreasing photocurrent because of the increasing spatial distance for electron transfer between two-type photosensitizers. Under optimum conditions, the PMB-based sensing system exhibited satisfying photocurrent responses toward target Kana within the working range from 50 to 5000 fM at a low detection limit of 29 fM. Impressively, the concept of a palindromic fragment-mediated primer-free biosensing strategy offers a new avenue for advanced development of efficient and convenient biodetection systems.
Assuntos
Bismuto/química , Compostos de Cádmio/química , Técnicas Eletroquímicas/métodos , Canamicina/análise , Nanopartículas Metálicas/química , Pontos Quânticos/química , Sulfetos/química , Animais , Antibacterianos/análise , Aptâmeros de Nucleotídeos/química , Aptâmeros de Nucleotídeos/genética , Técnicas Biossensoriais/métodos , DNA/química , DNA/genética , Técnicas Eletroquímicas/instrumentação , Eletrodos , Contaminação de Alimentos/análise , Ouro/química , Ouro/efeitos da radiação , Sequências Repetidas Invertidas , Luz , Limite de Detecção , Nanopartículas Metálicas/efeitos da radiação , Leite/química , Hibridização de Ácido Nucleico , Fotoquímica/métodosRESUMO
Pressure-based bioassays incorporating biomolecular recognition with a catalyzed gas-generation reaction have been developed for gas biosensors, but most involve poor sensitivity and are unsuitable for routine use. Herein we design an innovative gas pressure-based biosensing platform for the detection of Kanamycin (Kana) on polyaniline nanowires-functionalized reduced graphene oxide (PANI/rGO) framework by using platinum nanozyme-catalyzed gas generation. The signal was amplified by coupling with catalytic hairpin assembly (CHA) and strand-displacement amplification (SDA). Upon target Kana introduction, the analyte initially triggered a SDA reaction between hairpin DNA1 and hairpin DNA2, and then induced CHA conjugation between magnetic bead-labeled hairpin DNA3 (MB-H3) and platinum nanoparticle-labeled hairpin DNA4 (Pt-H4) to form a three-dimensional network. Numerous platinum nanoparticles (peroxidase-like nanozymes) were carried over with magnetic beads to reduce hydrogen peroxide into oxygen. The as-produced gas compressed PANI/rGO frameworks (modified to polyurethane sponge, used as the piezoelectric materials) in a homemade pressure-tight device, thus causing the increasing current of PANI/rGO sponge thanks to its deformation. The change in the current caused by the as-generated gas pressure was determined on an electrochemical workstation. Under optimum conditions, PANI/rGO sponge exhibited outstanding compressibility, stable signal-waveform output, fast response and recovery time (≈109 ms), and the current increased with the increasing Kana concentration within a dynamic working range of 0.2-50 pM at a detection limit of 0.063 pM. Good reproducibility, specificity, and acceptable precision were acquired for Kana analysis. In addition, the accuracy of this method was monitored to evaluate real milk samples with the well-matched results obtained by using the referenced Kana ELISA kit.
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A novel photoelectrochemical (PEC) enzyme immunoassay was designed for the ultrasensitive detection of alpha-fetoprotein (AFP) based on near-infrared (NIR) light-excited core-core-shell UCNP@Au@CdS upconversion nanospheres. Plasmonic gold (Au) between the sandwiched layers was not only utilized as an energy harvester for the collection of the incident light but also acted as an energy conveyor to transfer the energy from upconversion NaYF4:Yb3+,Er3+ (UCNP) to semiconductor CdS, thus exciting the efficient separation of electron-hole pairs by the generated H2O2 of enzyme immunoreaction under the irradiation of a 980 nm laser. By virtue of high catalytic activity of natural enzymes, gold nanoparticles heavily functionalized with glucose oxidase (GOx) and polyclonal anti-AFP antibody were utilized to generate H2O2. A sandwiched immunoreaction was first carried out in a monoclonal anti-AFP antibody-coated microplate by using an antibody-labeled gold nanoparticle as secondary antibody. Accompanying the gold nanoparticle, the carried GOx oxidized glucose in H2O2, thereby resulting in the enhanced photocurrent via capturing holes on the valence band of CdS to promote the separation of electron-hole pairs. Under optimum conditions, the NIR light-based PEC immunosensing system exhibited good photocurrent responses toward target AFP within the dynamic working range of 0.01-40 ng mL-1 at a detection limit of 5.3 pg mL-1. Moreover, the NIR light-based sensing platform had good reproducibility and high selectivity. Importantly, good well-matched results obtained from NIR light-based PEC immunoassay were acquired for the analysis of human serum specimens by using AFP ELISA kit as the reference.
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Compostos de Cádmio/química , Ouro/química , Técnicas Imunoenzimáticas/métodos , Substâncias Luminescentes/química , Nanosferas/química , Sulfetos/química , alfa-Fetoproteínas/análise , Anticorpos Imobilizados/química , Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Humanos , Raios Infravermelhos , Limite de Detecção , Nanosferas/ultraestrutura , Reprodutibilidade dos Testes , Espectrofotometria InfravermelhoRESUMO
Although Eucalyptus is widely planted in South China, whose effects on native biodiversity are unclear. The objective of this study was to quantify the richness and composition of understory plants in two contrasting Eucalyptus chronosequences in South China. One was in Zhangzhou City with plantation age of 2, 4, and 6 years after clear-cutting Chinese fir forests, while the other was in Heshan City with plantation age of 2, 3, and 24 years that reforested on barren lands. Results showed that the richness of understory plants and functional groups was not significantly altered in the Zhangzhou chronosequence, while increased in the 24-year-old plantations, with a significantly larger proportion of woody plants than the younger plantations for the Heshan chronosequence. Moreover, a higher richness of woody plants accompanied by a lower richness of herbaceous species was detected in the Zhangzhou chronosequence compared with the Heshan one. To balance the need for pulp production and plant diversity conservation, we suggest that intercropping approaches between exotic Eucalyptus plantations and native forests should be considered in the fast rotation Eucalyptus plantations. However, Eucalyptus plantations may be used as pioneer species to sustain ecosystem functioning for the degraded lands.
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Biodiversidade , Eucalyptus/fisiologia , Agricultura Florestal/métodos , China , Conservação dos Recursos Naturais , Florestas , Espécies Introduzidas , MadeiraRESUMO
A major impediment to the clinical translation of DNA tiling nanostructures is a technical bottleneck for the programmable assembly of DNA architectures with well-defined local geometry due to the inability to achieve both sufficient structural rigidity and a large framework. In this work, a Y-backbone was inserted into each face to construct a superlarge, sufficiently rigidified tetrahedral DNA nanostructure (called RDT) with extremely high efficiency. In RDT, the spatial size increased by 6.86-fold, and the structural rigidity was enhanced at least 4-fold, contributing to an â¼350-fold improvement in the resistance to nucleolytic degradation even without a protective coating. RDT can be mounted onto an artificial lipid-bilayer membrane with molecular-level precision and well-defined spatial orientation that can be validated using the fluorescence resonance energy transfer (FRET) assay. The spatial orientation of Y-shaped backbone-rigidified RDT is unachievable for conventional DNA polyhedrons and ensures a high level of precision in the geometric positioning of diverse biomolecules with an approximately homogeneous environment. In tests of RDT, surface-confined horseradish peroxidase (HRP) exhibited nearly 100% catalytic activity and targeting aptamer-immobilized gold nanoparticles showed 5.3-fold enhanced cellular internalization. Significantly, RDT exhibited a 27.5-fold enhanced structural stability in a bodily environment and did not induce detectable systemic toxicity.
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DNA , Transferência Ressonante de Energia de Fluorescência , Nanoestruturas , DNA/química , Nanoestruturas/química , Humanos , Peroxidase do Rábano Silvestre/química , Peroxidase do Rábano Silvestre/metabolismo , Animais , Conformação de Ácido Nucleico , Ouro/química , Bicamadas Lipídicas/química , CamundongosRESUMO
A photocurrent-polarity-switching photoelectrochemical (PEC) biosensor was developed for the ultrasensitive detection of tobramycin (TOB) through bipedal DNA walker amplification with hemin-induced photocurrent-polarity-switching using a laser-induced zinc oxide/graphene (ZnO/LIG) photoelectrode. Specifically, the ZnO/LIG photoelectrode was synthesized in situ by a laser direct writing (LDW) technique. In the presence of TOB, it reacted with HP1 and HP2 and the DNA walker response was activated to form a stable hemin/G-quadruplex. Furthermore, hemin induced a polarity shift in the photocurrent signal. The developed analytical platform exhibited excellent photoelectron transport performance of ZnO/LIG, the signal amplification effect of the DNA walker strategy, and the photocurrent-polarity-switching ability of hemin. Therefore, it demonstrated satisfying photocurrent responses to the target TOB within the working range of 20 nM-1.0 µM at a low detection limit of 5.43 nM. The PEC platform exhibited good stability, reproducibility, sufficient sensitivity and high selectivity for complex experimental samples. Moreover, the photocurrent-polarity-switching PEC biosensor improved the anti-interference ability and avoided false positives or negatives.
Assuntos
Técnicas Biossensoriais , Grafite , Óxido de Zinco , Técnicas Eletroquímicas , Hemina , Reprodutibilidade dos Testes , DNA/genética , Técnicas Biossensoriais/métodosRESUMO
Precisely modulating the Ru-O covalency in RuOx for enhanced stability in proton exchange membrane water electrolysis is highly desired. However, transition metals with d-valence electrons, which were doped into or alloyed with RuOx, are inherently susceptible to the influence of coordination environment, making it challenging to modulate the Ru-O covalency in a precise and continuous manner. Here, we first deduce that the introduction of lanthanide with gradually changing electronic configurations can continuously modulate the Ru-O covalency owing to the shielding effect of 5s/5p orbitals. Theoretical calculations confirm that the durability of Ln-RuOx following a volcanic trend as a function of Ru-O covalency. Among various Ln-RuOx, Er-RuOx is identified as the optimal catalyst and possesses a stability 35.5 times higher than that of RuO2. Particularly, the Er-RuOx-based device requires only 1.837 V to reach 3 A cm-2 and shows a long-term stability at 500 mA cm-2 for 100 h with a degradation rate of mere 37 µV h-1.