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1.
Proc Natl Acad Sci U S A ; 120(11): e2213698120, 2023 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-36897978

RESUMO

Locomotion is typically studied either in continuous media where bodies and legs experience forces generated by the flowing medium or on solid substrates dominated by friction. In the former, centralized whole-body coordination is believed to facilitate appropriate slipping through the medium for propulsion. In the latter, slip is often assumed minimal and thus avoided via decentralized control schemes. We find in laboratory experiments that terrestrial locomotion of a meter-scale multisegmented/legged robophysical model resembles undulatory fluid swimming. Experiments varying waves of leg stepping and body bending reveal how these parameters result in effective terrestrial locomotion despite seemingly ineffective isotropic frictional contacts. Dissipation dominates over inertial effects in this macroscopic-scaled regime, resulting in essentially geometric locomotion on land akin to microscopic-scale swimming in fluids. Theoretical analysis demonstrates that the high-dimensional multisegmented/legged dynamics can be simplified to a centralized low-dimensional model, which reveals an effective resistive force theory with an acquired viscous drag anisotropy. We extend our low-dimensional, geometric analysis to illustrate how body undulation can aid performance in non-flat obstacle-rich terrains and also use the scheme to quantitatively model how body undulation affects performance of biological centipede locomotion (the desert centipede Scolopendra polymorpha) moving at relatively high speeds (∼0.5 body lengths/sec). Our results could facilitate control of multilegged robots in complex terradynamic scenarios.

2.
Proc Natl Acad Sci U S A ; 119(31): e2200924119, 2022 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-35901212

RESUMO

Locomotion by shape changes or gas expulsion is assumed to require environmental interaction, due to conservation of momentum. However, as first noted in [J. Wisdom, Science 299, 1865-1869 (2003)] and later in [E. Guéron, Sci. Am. 301, 38-45 (2009)] and [J. Avron, O. Kenneth, New J. Phys, 8, 68 (2006)], the noncommutativity of translations permits translation without momentum exchange in either gravitationally curved spacetime or the curved surfaces encountered by locomotors in real-world environments. To realize this idea which remained unvalidated in experiments for almost 20 y, we show that a precision robophysical apparatus consisting of motors driven on curved tracks (and thereby confined to a spherical surface without a solid substrate) can self-propel without environmental momentum exchange. It produces shape changes comparable to the environment's inverse curvatures and generates movement of [Formula: see text] cm per gait. While this simple geometric effect predominates over short time, eventually the dissipative (frictional) and conservative forces, ubiquitous in real systems, couple to it to generate an emergent dynamics in which the swimming motion produces a force that is counter-balanced against residual gravitational forces. In this way, the robot both swims forward without momentum and becomes fixed in place with a finite momentum that can be released by ceasing the swimming motion. We envision that our work will be of use in a broad variety of contexts, such as active matter in curved space and robots navigating real-world environments with curved surfaces.

3.
Proc Natl Acad Sci U S A ; 119(30): e2113912119, 2022 07 26.
Artigo em Inglês | MEDLINE | ID: mdl-35857871

RESUMO

Studies of active matter-systems consisting of individuals or ensembles of internally driven and damped locomotors-are of interest to physicists studying nonequilibrium dynamics, biologists interested in individuals and swarm locomotion, and engineers designing robot controllers. While principles governing active systems on hard ground or within fluids are well studied, another class of systems exists at deformable interfaces. Such environments can display mixes of fluid-like and elastic features, leading to locomotor dynamics that are strongly influenced by the geometry of the surface, which, in itself, can be a dynamical entity. To gain insight into principles by which locomotors are influenced via a deformation field alone (and can influence other locomotors), we study robot locomotion on an elastic membrane, which we propose as a model of active systems on highly deformable interfaces. As our active agent, we use a differential driven wheeled robotic vehicle which drives straight on flat homogeneous surfaces, but reorients in response to environmental curvature. We monitor the curvature field-mediated dynamics of a single vehicle interacting with a fixed deformation as well as multiple vehicles interacting with each other via local deformations. Single vehicles display precessing orbits in centrally deformed environments, while multiple vehicles influence each other by local deformation fields. The active nature of the system facilitates a differential geometry-inspired mathematical mapping from the vehicle dynamics to those of test particles in a fictitious "spacetime," allowing further understanding of the dynamics and how to control agent interactions to facilitate or avoid multivehicle membrane-induced cohesion.


Assuntos
Locomoção , Robótica , Humanos
4.
Proc Natl Acad Sci U S A ; 119(12): e2120019119, 2022 03 22.
Artigo em Inglês | MEDLINE | ID: mdl-35298335

RESUMO

Experimental robobiological physics can bring insights into biological evolution. We present a development of hybrid analog/digital autonomous robots with mutable diploid dominant/recessive 6-byte genomes. The robots are capable of death, rebirth, and breeding. We map the quasi-steady-state surviving local density of the robots onto a multidimensional abstract "survival landscape." We show that robot death in complex, self-adaptive stress landscapes proceeds by a general lowering of the robotic genetic diversity, and that stochastically changing landscapes are the most difficult to survive.


Assuntos
Robótica , Animais , Mamíferos , Modelos Genéticos , Mutação , Dinâmica Populacional , Probabilidade , Seleção Genética
5.
Anal Chem ; 96(22): 9051-9059, 2024 06 04.
Artigo em Inglês | MEDLINE | ID: mdl-38776068

RESUMO

Surface-enhanced Raman spectroscopy (SERS) tags have the advantages of unique fingerprint vibration spectrum, ultranarrow spectral line widths, and weak photobleaching effect, showing great potential for bioimaging. However, SERS imaging is still hindered for further application due to its weak spontaneous Raman scattering, biomolecular signal interference, and long acquisition times. Here, we develop a novel SERS tag of the core (Au)-shell (N-doped graphene) structure (Au@NGs) with ultrastrong and stable Raman signal (2180 cm-1) in the cellular Raman-silent region (1800-2800 cm-1) through base-promoted oxidative decarboxylation of amino acids. Exploring the factors (metal salts, amino acids, catalysts, temperature, etc.) to obtain Au@NGs with the strongest Raman signal commonly requires more than 100,000 separate experiments, while that using an orthogonal array testing strategy is reduced to 56. The existence of deep charge transfer between the Au surface and C≡N-graphene is proved by theoretical calculations, which means the ultrastrong signal of Au@NGs is the joint effect of electromagnetic and chemical enhancement. The Au@NGs have a detection sensitivity down to a single-nanoparticle level, and high-speed and high-resolution cellular imaging (4453 pixels) is obtained within 10 s by global Raman imaging. The combination of Au@NGs-based tags with ultrastrong intrinsic Raman imaging capability and global imaging technology holds great promise for high-speed Raman imaging.


Assuntos
Ouro , Grafite , Análise Espectral Raman , Análise Espectral Raman/métodos , Ouro/química , Grafite/química , Humanos , Nanopartículas Metálicas/química , Propriedades de Superfície , Aminoácidos/análise , Aminoácidos/química
6.
Chemphyschem ; : e202400416, 2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38752794

RESUMO

Fossil fuels have clearly failed to meet people's growing energy needs due to their limited reserves, potential pollution of the environment, and high costs. The development of cleaner, renewable energy sources as well as secondary batteries for energy storage is imminent, in a modern society where energy demand is soaring. Sodium-ion batteries (SIBs) have become the focus of large-scale energy storage systems as a promising alternative to lithium-ion batteries. The development of SIBs relies on the construction of high performance electrode materials. The design of low cost and high performance anode materials is a key link in this regard. Copper-based anodes are characterized by high theoretical capacity, abundant reserves, low cost and environmental friendliness. A variety of copper-based anode materials, which include cobalt oxides, sulfides, selenides and phosphides, have been synthesized and evaluated in the scientific literature for sodium storage. In detail, the preparation methods, response mechanisms, strengths and weaknesses, the relationship between morphology structure and electrochemical performance are discussed, as well as highlighting strategies to improve the electrochemical performance of copper-based anode materials. Finally, we offer our perspective on the challenges and potential for the development of copper-based anodes as a means of developing practical and high performing SIBs.

7.
Sensors (Basel) ; 24(13)2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-39001147

RESUMO

With the development of data mining technology, the analysis of event-related potential (ERP) data has evolved from statistical analysis of time-domain features to data-driven techniques based on supervised and unsupervised learning. However, there are still many challenges in understanding the relationship between ERP components and the representation of familiar and unfamiliar faces. To address this, this paper proposes a model based on Dynamic Multi-Scale Convolution for group recognition of familiar and unfamiliar faces. This approach uses generated weight masks for cross-subject familiar/unfamiliar face recognition using a multi-scale model. The model employs a variable-length filter generator to dynamically determine the optimal filter length for time-series samples, thereby capturing features at different time scales. Comparative experiments are conducted to evaluate the model's performance against SOTA models. The results demonstrate that our model achieves impressive outcomes, with a balanced accuracy rate of 93.20% and an F1 score of 88.54%, outperforming the methods used for comparison. The ERP data extracted from different time regions in the model can also provide data-driven technical support for research based on the representation of different ERP components.


Assuntos
Potenciais Evocados , Reconhecimento Facial , Humanos , Potenciais Evocados/fisiologia , Reconhecimento Facial/fisiologia , Eletroencefalografia/métodos , Algoritmos , Face/fisiologia
8.
Mol Phylogenet Evol ; 188: 107903, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37574177

RESUMO

Yersinia spp. vary significantly in their ability to cause diseases that threaten public health. Their pathogenicity is frequently associated with increasing antimicrobial resistance (AMR) and various virulence factors. The aim of the study was to investigate the AMR genes, virulence factors, and genetic diversity of Yersinia strains isolated from meats and fish in Wenzhou in 2020 by using whole-genome sequencing (WGS). A total of 50 isolates were collected. The phylogenetic relationships among the Yersinia species were also analyzed using multilocus sequence typing (MLST), core genome multi-locus sequence typing (cgMLST), and single nucleotide polymorphism (SNP) analysis. According to the results, all the strains could be classified into five species, with most isolated from beef, followed by poultry, pork, and fish. AMR genes were identified in 23 strains. And the qnrD1 genes were all located in the Col3M plasmid. Virulence genes, such as yaxA, ystB, pla, and yplA, were also found in the 15 Y. enterocolitica strains. And this study also found the presence of icm/dot type IVB-related genes in one Yersinia massiliensis isolate. MLST analysis identified 43 sequence types (STs), 19 of which were newly detected in Yersinia. Moreover, cgMLST analysis revealed that no dense genotype clusters were formed (cgMLST 5341, 5344, 5346-5350, 5353-5390). Instead, the strains appeared to be dispersed over large distances, except when multiple isolates shared the same ST. Isolates Y4 and Y26 were closely related to strains originating from South Korea and Denmark. This study showed considerable diversity in Yersinia spp. isolated from local areas (Wenzhou City). The data generated in our study may enrich the molecular traceability database of Yersinia and provide a basis for the development of more effective antipathogen control strategies.


Assuntos
Antibacterianos , Fatores de Virulência , Animais , Bovinos , Fatores de Virulência/genética , Tipagem de Sequências Multilocus/métodos , Filogenia , Farmacorresistência Bacteriana/genética , Yersinia/genética , Variação Genética , Genoma Bacteriano
9.
Chemistry ; 29(15): e202203598, 2023 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-36527171

RESUMO

Charge-transfer (CT) engineering with inter-/intramolecular CT interactions by simple compositions has emerged as a universal and efficient way to construct organic functional materials. Stable organic radicals with unique physicochemical properties that cannot be realized in closed-shell molecules, have been widely demonstrated to be ideal building blocks to construct versatile organic CT materials. This concept article provides a brief overview of the advances in the design, structure and property of stable organic radicals-based CT molecular functional materials, and the strategy for the generation of these materials is also highlighted. First, radicals are introduced as open-shell donors or acceptors, with a focus on their importance and uniqueness in improving electrical, magnetic and optical properties of CT functional materials. Additionally, CT interactions in stable radical dimers and trimers are further discussed systematically. Finally, the challenges are summarized and perspectives for future development of stable organic radicals-based CT functional materials are provided.

10.
Nano Lett ; 22(20): 8339-8345, 2022 10 26.
Artigo em Inglês | MEDLINE | ID: mdl-36222760

RESUMO

Reducing heat dissipation plays an indispensable role in boosting the magnetothermal effect but has received scant attention. Herein, a magnetothermal aerogel (MA) combining an efficient magnetothermal convertor for heat generation and a highly porous aerogel for reducing heat dissipation is developed. Such a heat confinement MA shows a large thermal resistance and high infrared absorption that can effectively confine the heat by regulating interior thermal conduction and radiation, exhibiting a supramagnetothermal effect. In addition, a waterproof beeswax coated MA achieves negligible heat loss and a supramagnetothermal effect even in high-thermal-diffusion aqueous media. As a proof of concept, a synthesized heat-triggered nitric oxide (NO) precursor is integrated into an MA, and the rapid NO generation (∼22 µM/min) resulting in an antibacterial effect further verifies the supramagnetothermal effect of the MA. This work provides an efficient strategy to promote the magnetothermal effect and offers inspiration for building a heat-triggering system.


Assuntos
Temperatura Alta , Óxido Nítrico , Condutividade Térmica , Água , Antibacterianos
11.
Small ; 18(11): e2104876, 2022 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-35119209

RESUMO

Lithium (Li) metal is an excellent anode of Li ion batteries because of its high theoretical capacity and the low redox potential compared to other anodes. However, the uncontrollable growth of Li dendrites still incurs serious safety issues and poor electrochemical performances, leading to its limited practical application. An oxygen and boron codoped honeycomb carbon skeleton (OBHcCs) is reported and a stable Li metal-based anode is realized. It can be coated on a copper foil substrate to be used as a current collector for a dendrite-free Li metal anode. OBHcCs effectively reduces the local current density owing to the high surface area and inhibits Li dendrite growth, which is explored by scanning electron microscopy and an X-ray photoelectron spectra depth profile. The abundant lithiophilic oxygen and boron-containing functional groups reduce the potential barrier of nucleation and lead to the homogeneous Li ions flux as confirmed by the density functional theories. Therefore, the Li metal anode based on OBHcCs (OBHcCs@Li) stably runs for 700 h in a symmetric cell with a Li stripping capacity of 1 mAh cm-2 at 1 mA cm-2 . Furthermore, the OBHcCs@Li|LiFePO4 full cell shows a good capacity retention of 84.6% with a high coulombic efficiency of 99.6% at 0.5 C for 500 cycles.

12.
Angew Chem Int Ed Engl ; 61(21): e202202571, 2022 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-35266269

RESUMO

Designing organic charge-transfer (CT) cocrystals for efficient solar-thermal conversion is a long-sought goal but remains challenging. Here we construct a unique CT cocrystal by using a persistent 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS+. ) as the electron acceptor. The strong persistency and electron affinity of ABTS+. endow a high degree of electron delocalization between ABTS+. and the 3,3',5,5'-tetramethylbenzidine donor. Together with the intrinsic long-wavelength absorption of ABTS+. , the synthesized cocrystal can effectively capture the full solar spectrum and show distinguished photothermal efficiency. Such a cocrystal is further used for solar-driven interfacial evaporation, and a high evaporation rate of 1.407 kg m-2 h-1 and a remarkable solar-to-vapor efficiency of 97.0 % have been achieved upon 1 sun irradiation. This work indicates the enormous prospects for charge transfer-based functional materials through rational radical cation engineering.

13.
Phys Rev Lett ; 126(10): 108002, 2021 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-33784150

RESUMO

We present an ecology-inspired form of active matter consisting of a robot swarm. Each robot moves over a planar dynamic resource environment represented by a large light-emitting diode array in search of maximum light intensity; the robots deplete (dim) locally by their presence the local light intensity and seek maximum light intensity. Their movement is directed along the steepest local light intensity gradient; we call this emergent symmetry breaking motion "field drive." We show there emerge dynamic and spatial transitions similar to gas, crystalline, liquid, glass, and jammed states as a function of robot density, resource consumption rates, and resource recovery rates. Paradoxically the nongas states emerge from smooth, flat resource landscapes, not rough ones, and each state can directly move to a glassy state if the resource recovery rate is slow enough, at any robot density.

14.
BMC Infect Dis ; 21(1): 127, 2021 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-33514323

RESUMO

BACKGROUND: To investigate the CT imaging and clinical features of three atypical presentations of coronavirus disease 2019 (COVID-19), namely (1) asymptomatic, (2) CT imaging-negative, and (3) re-detectable positive (RP), during all disease stages. METHODS: A consecutive cohort of 79 COVID-19 patients was retrospectively recruited from five independent institutions. For each presentation type, all patients were classified into atypical vs. typical groups (i.e., asymptomatic vs.symptomatic, CT imaging-negative vs. CT imaging-positive, and RP and non-RP,respectively). The chi-square test, Student's t test, and Kruskal-Wallis H test were performed to compare CT imaging and clinical features of atypical vs. typical patients for all three presentation categories. RESULTS: In our COVID-19 cohort, we found 12.7% asymptomatic patients, 13.9% CT imaging-negative patients, and 8.9% RP patients. The asymptomatic patients had fewer hospitalization days (P=0.043), lower total scores for bilateral lung involvement (P< 0.001), and fewer ground-glass opacities (GGOs) in the peripheral area (P< 0.001) than symptomatic patients. The CT imaging-negative patients were younger (P=0.002), had a higher lymphocyte count (P=0.038), had a higher lymphocyte rate (P=0.008), and had more asymptomatic infections (P=0.002) than the CT imaging-positive patients. The RP patients with moderate COVID-19 had lower total scores of for bilateral lung involvement (P=0.030) and a smaller portion of the left lung affected (P=0.024) than non-RP patients. Compared to their first hospitalization, RP patients had a shorter hospitalization period (P< 0.001) and fewer days from the onset of illness to last RNA negative conversion (P< 0.001) at readmission. CONCLUSIONS: Significant CT imaging and clinical feature differences were found between atypical and typical COVID-19 patients for all three atypical presentation categories investigated in this study, which may help provide complementary information for the effective management of COVID-19.


Assuntos
COVID-19/diagnóstico por imagem , Pulmão/diagnóstico por imagem , Radiografia Torácica , Tomografia Computadorizada por Raios X , Adulto , Infecções Assintomáticas , COVID-19/epidemiologia , China/epidemiologia , Feminino , Hospitalização , Humanos , Masculino , Pessoa de Meia-Idade , Readmissão do Paciente , Estudos Retrospectivos , SARS-CoV-2
15.
Eur Radiol ; 30(9): 4893-4902, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32300971

RESUMO

OBJECTIVES: Rapid and accurate diagnosis of coronavirus disease 2019 (COVID-19) is critical during the epidemic. We aim to identify differences in CT imaging and clinical manifestations between pneumonia patients with and without COVID-19, and to develop and validate a diagnostic model for COVID-19 based on radiological semantic and clinical features alone. METHODS: A consecutive cohort of 70 COVID-19 and 66 non-COVID-19 pneumonia patients were retrospectively recruited from five institutions. Patients were divided into primary (n = 98) and validation (n = 38) cohorts. The chi-square test, Student's t test, and Kruskal-Wallis H test were performed, comparing 1745 lesions and 67 features in the two groups. Three models were constructed using radiological semantic and clinical features through multivariate logistic regression. Diagnostic efficacies of developed models were quantified by receiver operating characteristic curve. Clinical usage was evaluated by decision curve analysis and nomogram. RESULTS: Eighteen radiological semantic features and seventeen clinical features were identified to be significantly different. Besides ground-glass opacities (p = 0.032) and consolidation (p = 0.001) in the lung periphery, the lesion size (1-3 cm) is also significant for the diagnosis of COVID-19 (p = 0.027). Lung score presents no significant difference (p = 0.417). Three diagnostic models achieved an area under the curve value as high as 0.986 (95% CI 0.966~1.000). The clinical and radiological semantic models provided a better diagnostic performance and more considerable net benefits. CONCLUSIONS: Based on CT imaging and clinical manifestations alone, the pneumonia patients with and without COVID-19 can be distinguished. A model composed of radiological semantic and clinical features has an excellent performance for the diagnosis of COVID-19. KEY POINTS: • Based on CT imaging and clinical manifestations alone, the pneumonia patients with and without COVID-19 can be distinguished. • A diagnostic model for COVID-19 was developed and validated using radiological semantic and clinical features, which had an area under the curve value of 0.986 (95% CI 0.966~1.000) and 0.936 (95% CI 0.866~1.000) in the primary and validation cohorts, respectively.


Assuntos
Betacoronavirus , Infecções por Coronavirus/diagnóstico por imagem , Pneumonia Viral/diagnóstico por imagem , Adolescente , Adulto , Idoso , COVID-19 , Feminino , Humanos , Pulmão/patologia , Masculino , Pessoa de Meia-Idade , Nomogramas , Pandemias , Curva ROC , Estudos Retrospectivos , SARS-CoV-2 , Semântica , Tomografia Computadorizada por Raios X/métodos , Adulto Jovem
16.
Anal Chem ; 91(2): 1516-1523, 2019 01 15.
Artigo em Inglês | MEDLINE | ID: mdl-30567424

RESUMO

In this work, an electrochemiluminescent (ECL) biosensor was constructed on the basis of amino-modified 3,4,9,10-perylenetetracarboxylic dianhydride/luminol (PTC-NH2/Lu) nanocomposite as emitter and bipedal DNA walker signal amplification strategy for ultrasensitive detection of microRNA-21 (miRNA-21). The PTC-NH2/Lu nanocomposite was prepared as signal tag via π-π stacking molecular assembly, in which amino-modified 3,4,9,10-perylenetetracarboxylic dianhydride (PTC-NH2) as a novel coreaction accelerator significantly enhanced the ECL emission of luminol-H2O2 system. Moreover, target miRNA-21 triggered bipedal DNA walker was powered by toehold-mediated strand displacement reaction (TSDR) for signal amplification. Consequently, the proposed ECL biosensor achieved ultrasensitive detection of miRNA-21 with a linear range from 100 aM to 100 pM and a limit of detection of 33 aM. Simultaneously, the biosensor was also successfully applied to detect target miRNA-21 in lysates from human cancer cells. As a result, this work constructed a new signal amplification platform, exhibiting great application potential in biomedical analysis and early clinical diagnostics.


Assuntos
Técnicas Biossensoriais/métodos , Limite de Detecção , Luminescência , Luminol/química , MicroRNAs/análise , Nanocompostos/química , Perileno/química , Eletroquímica , Células HeLa , Humanos , Células MCF-7 , MicroRNAs/química
17.
Anal Chem ; 91(5): 3710-3716, 2019 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-30724078

RESUMO

Apart from the reported energy transfer mechanism of aggregation-induced electrochemiluminescence (AI-ECL) enhancement, a new strategy named restriction of intramolecular motions-driven ECL (RIM-ECL) enhancement is first proposed based on the phenomenon of a very strong electrochemiluminescence observed on the hexagonal tetraphenylethylene microcrystals (TPE MCs) in aqueous solution. Compared to TPE in molecule-isolation state with faint ECL, TPE in aggregate state (TPE MCs) showed a significantly enhanced ECL that was due to the restriction of intramolecular motions (RIM). Inspired by the unique luminescence characteristic of TPE MCs, we integrated the novel ECL emitter of TPE MCs and target-activated bipedal DNA walker together to fabricate a sensitive "off-on" ECL biosensor for Mucin 1 (MUC1) assay, which exhibited desirable linear response for a concentration scope from 1 fg/mL to 1 ng/mL with a low detection limit of 0.29 fg/mL. The RIM enhanced ECL demonstrated by the TPE MCs provides a new chapter in the exploration of aggregated organic emitters for further applications.


Assuntos
Técnicas Eletroquímicas/métodos , Medições Luminescentes/métodos , Movimento (Física) , Mucina-1/análise , Estilbenos/química , Animais , Técnicas Biossensoriais , Cristalização , Humanos , Limite de Detecção , Luminescência , Soluções
18.
Anal Chem ; 91(5): 3681-3686, 2019 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-30698003

RESUMO

A sensitive electrochemiluminescence (ECL) biosensor was developed for glutathione (GSH) detection based on a novel Ru(bpy)2(cpaphen)2+/TPrA/TiO2 ternary ECL system with Mn2+ as substitute target for signal amplification. Specifically, the TiO2 nanoneedles (TiO2 NNs) were used as the coreaction accelerator for the first time to promote the oxidation process of coreactant tripropylamine (TPrA) in the anode and significantly increase the ECL signal of Ru(bpy)2(cpaphen)2+ for an amplified initial signal. Meanwhile, a novel target conversion strategy for GSH was developed by reducing MnO2 nanosheets to Mn2+ as a substitute target, which played the role of a coenzyme factor for cleaving DNA double strands intercalated with Ru(bpy)2(cpaphen)2+ to markedly weaken initial signal. As a result, the novel "on-off" biosensor achieved a sensitive detection of GSH range from 5 µM to 215 µM with a detection limit of 0.33 µM. Importantly, the proposed strategy enriched the application of Ru complex and TPrA ECL system in bioanalytical applications, and provided a new signal amplification strategy for bioactive small molecules.


Assuntos
Técnicas Biossensoriais/métodos , Complexos de Coordenação/sangue , Glutationa/análise , Poliaminas/química , Rutênio/química , Titânio/química , Técnicas Biossensoriais/normas , Quebras de DNA de Cadeia Dupla , Técnicas Eletroquímicas , Substâncias Intercalantes , Limite de Detecção , Manganês
19.
Anal Chem ; 91(14): 8762-8766, 2019 07 16.
Artigo em Inglês | MEDLINE | ID: mdl-31241905

RESUMO

Noble metals with strong plasmons have been widely used as enhancement substrates for molecule identification. However, cyanide, a toxic and important signaling molecule with a corrosive nature to noble metals, makes direct recognition challenging. Herein a novel superstable magnetic graphene-isolated AuCo nanocrystal (MACG) has been designed. Such graphene isolation enables superior stability without corrosion. Moreover, unexpectedly, although graphene isolated direct contact between Au and cyanide, their interaction was transferable and remained, which gifted MACGs direct cyanide capture capability with no specific ligands needed. Density functional theory calculations and natural bond orbital analysis indicated that the graphene isolation only slightly affected the charge transfer and that a relatively strong interaction was maintained between Au and cyanide. MACGs were utilized for efficient cyanide capture and clearance in various hydrologic environments and sensitive in vivo cyanide capture in C. elegans infected with P. aeruginosa, a pathogen with cyanide as the biomarker, indicating promise for various applications.


Assuntos
Cobalto/química , Cianetos/isolamento & purificação , Ouro/química , Grafite/química , Nanopartículas/química , Animais , Caenorhabditis elegans/microbiologia , Células HeLa , Humanos , Imãs/química
20.
J Am Chem Soc ; 138(41): 13473-13476, 2016 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-27704816

RESUMO

We report a simple strategy for the creation of large-area nanoporous hybrid films of silica, carbon, and gold on polyethylene terephthalate via photothermal processing. This method enables the selective heating of light-absorbing thin films on low-temperature substrates using sub-millisecond light pulses generated by a xenon flash lamp. The film contains gold nanoparticles as the nanoheaters to convert light energy to heat, a sacrificial block copolymer surfactant to generate mesopores, and cross-linked polyhedral oligomeric silsesquioxane as the silica source to form the skeleton of the porous structure. Hierarchical porous structures are achieved in the films after photothermal treatment, with uniform mesopores (44-48 nm) on the surface and interconnected macropores (>50 nm) underneath resulting from a foaming effect during release of gaseous decomposition products. The loading of gold nanoparticles is up to 43 wt % in the product, with less than 2 wt % organic residue. This rapid and large-area process for the synthetis of porous structures is compatible with roll-to-roll manufacturing for the fabrication of flexible devices.

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