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1.
Chem Rev ; 123(6): 2737-2831, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36898130

RESUMO

Confined fluids and electrolyte solutions in nanopores exhibit rich and surprising physics and chemistry that impact the mass transport and energy efficiency in many important natural systems and industrial applications. Existing theories often fail to predict the exotic effects observed in the narrowest of such pores, called single-digit nanopores (SDNs), which have diameters or conduit widths of less than 10 nm, and have only recently become accessible for experimental measurements. What SDNs reveal has been surprising, including a rapidly increasing number of examples such as extraordinarily fast water transport, distorted fluid-phase boundaries, strong ion-correlation and quantum effects, and dielectric anomalies that are not observed in larger pores. Exploiting these effects presents myriad opportunities in both basic and applied research that stand to impact a host of new technologies at the water-energy nexus, from new membranes for precise separations and water purification to new gas permeable materials for water electrolyzers and energy-storage devices. SDNs also present unique opportunities to achieve ultrasensitive and selective chemical sensing at the single-ion and single-molecule limit. In this review article, we summarize the progress on nanofluidics of SDNs, with a focus on the confinement effects that arise in these extremely narrow nanopores. The recent development of precision model systems, transformative experimental tools, and multiscale theories that have played enabling roles in advancing this frontier are reviewed. We also identify new knowledge gaps in our understanding of nanofluidic transport and provide an outlook for the future challenges and opportunities at this rapidly advancing frontier.

2.
Nat Mater ; 22(12): 1453-1462, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37620646

RESUMO

Robots have components that work together to accomplish a task. Colloids are particles, usually less than 100 µm, that are small enough that they do not settle out of solution. Colloidal robots are particles capable of functions such as sensing, computation, communication, locomotion and energy management that are all controlled by the particle itself. Their design and synthesis is an emerging area of interdisciplinary research drawing from materials science, colloid science, self-assembly, robophysics and control theory. Many colloidal robot systems approach synthetic versions of biological cells in autonomy and may find ultimate utility in bringing these specialized functions to previously inaccessible locations. This Perspective examines the emerging literature and highlights certain design principles and strategies towards the realization of colloidal robots.

3.
Nano Lett ; 23(3): 916-924, 2023 02 08.
Artigo em Inglês | MEDLINE | ID: mdl-36651830

RESUMO

Gibberellins (GAs) are a class of phytohormones, important for plant growth, and very difficult to distinguish because of their similarity in chemical structures. Herein, we develop the first nanosensors for GAs by designing and engineering polymer-wrapped single-walled carbon nanotubes (SWNTs) with unique corona phases that selectively bind to bioactive GAs, GA3 and GA4, triggering near-infrared (NIR) fluorescence intensity changes. Using a new coupled Raman/NIR fluorimeter that enables self-referencing of nanosensor NIR fluorescence with its Raman G-band, we demonstrated detection of cellular GA in Arabidopsis, lettuce, and basil roots. The nanosensors reported increased endogenous GA levels in transgenic Arabidopsis mutants that overexpress GA and in emerging lateral roots. Our approach allows rapid spatiotemporal detection of GA across species. The reversible sensor captured the decreasing GA levels in salt-treated lettuce roots, which correlated remarkably with fresh weight changes. This work demonstrates the potential for nanosensors to solve longstanding problems in plant biotechnology.


Assuntos
Arabidopsis , Nanotubos de Carbono , Giberelinas/química , Giberelinas/metabolismo , Reguladores de Crescimento de Plantas/metabolismo , Arabidopsis/metabolismo , Nanotubos de Carbono/química , Fluorescência , Corantes
4.
Nanotechnology ; 34(11)2023 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-36595236

RESUMO

Quantum emitters in two-dimensional hexagonal boron nitride (hBN) are of significant interest because of their unique photophysical properties, such as single-photon emission at room temperature, and promising applications in quantum computing and communications. The photoemission from hBN defects covers a wide range of emission energies but identifying and modulating the properties of specific emitters remain challenging due to uncontrolled formation of hBN defects. In this study, more than 2000 spectra are collected consisting of single, isolated zero-phonon lines (ZPLs) between 1.59 and 2.25 eV from diverse sample types. Most of ZPLs are organized into seven discretized emission energies. All emitters exhibit a range of lifetimes from 1 to 6 ns, and phonon sidebands offset by the dominant lattice phonon in hBN near 1370 cm-1. Two chemical processing schemes are developed based on water and boric acid etching that generate or preferentially interconvert specific emitters, respectively. The identification and chemical interconversion of these discretized emitters should significantly advance the understanding of solid-state chemistry and photophysics of hBN quantum emission.

5.
J Math Biol ; 86(1): 11, 2022 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-36478092

RESUMO

Recent progress in nanotechnology-enabled sensors that can be placed inside of living plants has shown that it is possible to relay and record real-time chemical signaling stimulated by various abiotic and biotic stresses. The mathematical form of the resulting local reactive oxygen species (ROS) wave released upon mechanical perturbation of plant leaves appears to be conserved across a large number of species, and produces a distinct waveform from other stresses including light, heat and pathogen-associated molecular pattern (PAMP)-induced stresses. Herein, we develop a quantitative theory of the local ROS signaling waveform resulting from mechanical stress in planta. We show that nonlinear, autocatalytic production and Fickian diffusion of H2O2 followed by first order decay well describes the spatial and temporal properties of the waveform. The reaction-diffusion system is analyzed in terms of a new approximate solution that we introduce for such problems based on a single term logistic function ansatz. The theory is able to describe experimental ROS waveforms and degradation dynamics such that species-dependent dimensionless wave velocities are revealed, corresponding to subtle changes in higher moments of the waveform through an apparently conserved signaling mechanism overall. This theory has utility in potentially decoding other stress signaling waveforms for light, heat and PAMP-induced stresses that are similarly under investigation. The approximate solution may also find use in applied agricultural sensing, facilitating the connection between measured waveform and plant physiology.


Assuntos
Peróxido de Hidrogênio , Estresse Mecânico
6.
Small ; 17(48): e2006752, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-33675290

RESUMO

Carbon nanomaterials have extraordinary thermal properties, such as high conductivity and stability. Nanocarbon combined with phase change materials (PCMs) can yield exceptionally high thermal effusivity composites optimal for thermal energy harvesting. The progress in synthesis and processing of high effusivity materials, and their application in resonant energy harvesting from temperature variations is reviewed.


Assuntos
Temperatura Alta , Nanoestruturas , Carbono , Temperatura , Condutividade Térmica
7.
Small ; 17(31): e2100540, 2021 08.
Artigo em Inglês | MEDLINE | ID: mdl-34176216

RESUMO

Vitamins such as riboflavin and ascorbic acid are frequently utilized in a range of biomedical applications as drug delivery targets, fluidic tracers, and pharmaceutical excipients. Sensing these biochemicals in the human body has the potential to significantly advance medical research and clinical applications. In this work, a nanosensor platform consisting of single-walled carbon nanotubes (SWCNTs) with nanoparticle corona phases engineered to allow for the selective molecular recognition of ascorbic acid and riboflavin, is developed. The study provides a methodological framework for the implementation of colloidal SWCNT nanosensors in an intraperitoneal SKH1-E murine model by addressing complications arising from tissue absorption and scattering, mechanical perturbations, as well as sensor diffusion and interactions with the biological environment. Nanosensors are encapsulated in a polyethylene glycol diacrylate hydrogel and a diffusion model is utilized to validate analyte transport and sensor responses to local concentrations at the boundary. Results are found to be reproducible and stable after exposure to 10% mouse serum even after three days of in vivo implantation. A geometrical encoding scheme is used to reference sensor pairs, correcting for in vivo optical and mechanical artifacts, resulting in an order of magnitude improvement of p-value from 0.084 to 0.003 during analyte sensing.


Assuntos
Nanopartículas , Nanotubos de Carbono , Animais , Corantes , Camundongos , Vitaminas
8.
Nano Lett ; 20(5): 3067-3078, 2020 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-32058726

RESUMO

Nanostructured fibers provide a basis for a unique class of multifunctional textiles, composites, and membrane applications, including those capable of chromatic modulating because of their high aspect ratio, surface area, and processing capability. Here in, we utilize two-dimensional (2D) materials including molybdenum disulfide (MoS2) and hexagonal boron nitride (hBN) to generate single layer Archimedean scroll fibers, possessing cross sections formed from a single 2D molecular layer. Chemical vapor deposited (CVD) monolayer MoS2 (0.29-0.33% in volume) and 226-259 nm-thick poly(methyl methacrylate) (PMMA) were used to create Bragg reflector fibers, exploiting the anisotropic function, exhibiting reflection at 630-709 nm, and verifying the highly ordered nanoinclusions. The Bragg reflectors show a memory response to heating and cooling, which switches the reflection wavelength from 629 to 698 nm. We simulate the reflection and transmission spectra of MoS2/PMMA and MoS2/polydimethylsiloxane layered composites to provide the design of scroll fiber composites using the transfer matrix methods. Moreover, we demonstrate the incorporation of a few-layer CVD hBN into the scroll fiber composite that emits photons at 576 nm. The highly oriented layered structures extend the capability of the fiber nanocomposites to take advantage of anisotropic optical, electrical, and thermal properties unique to 2D materials.

9.
Nat Mater ; 17(11): 1005-1012, 2018 11.
Artigo em Inglês | MEDLINE | ID: mdl-30353088

RESUMO

Graphene and other two-dimensional materials possess desirable mechanical, electrical and chemical properties for incorporation into or onto colloidal particles, potentially granting them unique electronic functions. However, this application has not yet been realized, because conventional top-down lithography scales poorly for producing colloidal solutions. Here, we develop an 'autoperforation' technique that provides a means of spontaneous assembly for surfaces composed of two-dimensional molecular scaffolds. Chemical vapour deposited two-dimensional sheets can autoperforate into circular envelopes when sandwiching a microprinted polymer composite disk of nanoparticle ink, allowing liftoff into solution and simultaneous assembly. The resulting colloidal microparticles have two independently addressable, external Janus faces that we show can function as an intraparticle array of vertically aligned, two-terminal electronic devices. Such particles demonstrate remarkable chemical and mechanical stability and form the basis of particulate electronic devices capable of collecting and storing information about their surroundings, extending nanoelectronics into previously inaccessible environments.

10.
Small ; 14(44): e1802086, 2018 11.
Artigo em Inglês | MEDLINE | ID: mdl-30191658

RESUMO

The ability to control the subcellular localization of nanoparticles within living plants offers unique advantages for targeted biomolecule delivery and enables important applications in plant bioengineering. However, the mechanism of nanoparticle transport past plant biological membranes is poorly understood. Here, a mechanistic study of nanoparticle cellular uptake into plant protoplasts is presented. An experimentally validated mathematical model of lipid exchange envelope penetration mechanism for protoplasts, which predicts that the subcellular distribution of nanoparticles in plant cells is dictated by the particle size and the magnitude of the zeta potential, is advanced. The mechanism is completely generic, describing nanoparticles ranging from quantum dots, gold and silica nanoparticles, nanoceria, and single-walled carbon nanotubes (SWNTs). In addition, the use of imaging flow cytometry to investigate the influence of protoplasts' morphological characteristics on nanoparticle uptake efficiency is demonstrated. Using DNA-wrapped SWNTs as model nanoparticles, it is found that glycerolipids, the predominant lipids in chloroplast membranes, exhibit stronger lipid-nanoparticle interaction than phospholipids, the major constituent in protoplast membrane. This work can guide the rational design of nanoparticles for targeted delivery into specific compartments within plant cells without the use of chemical or mechanical aid, potentially enabling various plant engineering applications.


Assuntos
Nanoestruturas/química , Protoplastos/metabolismo , Citometria de Fluxo , Nanotubos de Carbono/química
11.
Small ; 14(13): e1703727, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29411935

RESUMO

The 2D semiconductor monolayer transition metal dichalcogenides, WS2 and MoS2 , are grown by chemical vapor deposition (CVD) and assembled by sequential transfer into vertical layered heterostructures (VLHs). Insulating hBN, also produced by CVD, is utilized to control the separation between WS2 and MoS2 by adjusting the layer number, leading to fine-scale tuning of the interlayer interactions within the VLHs. The interlayer interactions are studied by photoluminescence (PL) spectroscopy and are demonstrated to be highly sensitive to the input excitation power. For thin hBN separators (one to two layers), the total PL emission switches from quenching to enhancement by increasing the laser power. Femtosecond broadband transient absorption measurements demonstrate that the increase in PL quantum yield results from Förster energy transfer from MoS2 to WS2 . The PL signal is further enhanced at cryogenic temperatures due to the suppressed nonradiative decay channels. It is shown that (4 ± 1) layers of hBN are optimum for obtaining PL enhancement in the VLHs. Increasing thickness beyond this causes the enhancement factor to diminish, with the WS2 and MoS2 then behaving as isolated noninteracting monolayers. These results indicate how controlling the exciton generation rate influences energy transfer and plays an important role in the properties of VLHs.

12.
Nat Mater ; 16(2): 264-272, 2017 02.
Artigo em Inglês | MEDLINE | ID: mdl-27798623

RESUMO

Plant nanobionics aims to embed non-native functions to plants by interfacing them with specifically designed nanoparticles. Here, we demonstrate that living spinach plants (Spinacia oleracea) can be engineered to serve as self-powered pre-concentrators and autosamplers of analytes in ambient groundwater and as infrared communication platforms that can send information to a smartphone. The plants employ a pair of near-infrared fluorescent nanosensors-single-walled carbon nanotubes (SWCNTs) conjugated to the peptide Bombolitin II to recognize nitroaromatics via infrared fluorescent emission, and polyvinyl-alcohol functionalized SWCNTs that act as an invariant reference signal-embedded within the plant leaf mesophyll. As contaminant nitroaromatics are transported up the roots and stem into leaf tissues, they accumulate in the mesophyll, resulting in relative changes in emission intensity. The real-time monitoring of embedded SWCNT sensors also allows residence times in the roots, stems and leaves to be estimated, calculated to be 8.3 min (combined residence times of root and stem) and 1.9 min mm-1 leaf, respectively. These results demonstrate the ability of living, wild-type plants to function as chemical monitors of groundwater and communication devices to external electronics at standoff distances.


Assuntos
Engenharia Genética/métodos , Hidrocarbonetos Aromáticos/metabolismo , Compostos de Nitrogênio/metabolismo , Peptídeos/metabolismo , Plantas Geneticamente Modificadas/fisiologia , Spinacia oleracea/fisiologia , Biônica/métodos , Substâncias Explosivas/análise , Hidrocarbonetos Aromáticos/análise , Raios Infravermelhos , Nanotubos de Carbono/química , Compostos de Nitrogênio/análise , Peptídeos/genética
13.
Nano Lett ; 17(12): 7951-7961, 2017 12 13.
Artigo em Inglês | MEDLINE | ID: mdl-29148804

RESUMO

The engineering of living plants for visible light emission and sustainable illumination is compelling because plants possess independent energy generation and storage mechanisms and autonomous self-repair. Herein, we demonstrate a plant nanobionic approach that enables exceptional luminosity and lifetime utilizing four chemically interacting nanoparticles, including firefly luciferase conjugated silica (SNP-Luc), d-luciferin releasing poly(lactic-co-glycolic acid) (PLGA-LH2), coenzyme A functionalized chitosan (CS-CoA) and semiconductor nanocrystal phosphors for longer wavelength modulation. An in vitro kinetic model incorporating the release rates of the nanoparticles is developed to maximize the chemiluminescent lifetimes to exceed 21.5 h. In watercress (Nasturtium officinale) and other species, the nanoparticles circumvent limitations such as luciferin toxicity above 400 µM and colocalization of enzymatic reactions near high adenosine triphosphate (ATP) production. Pressurized bath infusion of nanoparticles (PBIN) is introduced to deliver a mixture of nanoparticles to the entire living plant, well described using a nanofluidic mathematical model. We rationally design nanoparticle size and charge to control localization within distinct tissues compartments with 10 nm nanoparticles localizing within the leaf mesophyll and stomata guard cells, and those larger than 100 nm segregated in the leaf mesophyll. The results are mature watercress plants that emit greater than 1.44 × 1012 photons/sec or 50% of 1 µW commercial luminescent diodes and modulate "off" and "on" states by chemical addition of dehydroluciferin and coenzyme A, respectively. We show that CdSe nanocrystals can shift the chemiluminescent emission to 760 nm enabling near-infrared (nIR) signaling. These results advance the viability of nanobionic plants as self-powered photonics, direct and indirect light sources.


Assuntos
Brassicaceae/metabolismo , Substâncias Luminescentes/química , Nanopartículas/química , Nasturtium/metabolismo , Spinacia oleracea/metabolismo , Brassicaceae/química , Compostos de Cádmio/química , Compostos de Cádmio/metabolismo , Quitosana/análogos & derivados , Quitosana/química , Quitosana/metabolismo , Coenzima A/química , Coenzima A/metabolismo , Luciferina de Vaga-Lumes/química , Luciferina de Vaga-Lumes/metabolismo , Luz , Luciferases/química , Luciferases/metabolismo , Luminescência , Substâncias Luminescentes/metabolismo , Nasturtium/química , Folhas de Planta/química , Folhas de Planta/metabolismo , Copolímero de Ácido Poliláctico e Ácido Poliglicólico/química , Radiação , Compostos de Selênio/química , Compostos de Selênio/metabolismo , Spinacia oleracea/química
14.
J Am Chem Soc ; 139(46): 16791-16802, 2017 11 22.
Artigo em Inglês | MEDLINE | ID: mdl-29052988

RESUMO

Single-stranded DNA oligonucleotides have unique, and in some cases sequence-specific molecular interactions with the surface of carbon nanotubes that remain the subject of fundamental study. In this work, we observe and analyze a generic, ionic strength-mediated phase transition exhibited by over 25 distinct oligonucleotides adsorbed to single-walled carbon nanotubes (SWCNTs) in colloidal suspension. The phase transition occurs as monovalent salts are used to modify the ionic strength from 500 mM to 1 mM, causing a reversible reduction in the fluorescence quantum yield by as much as 90%. The phase transition is only observable by fluorescence quenching within a window of pH and in the presence of dissolved O2, but occurs independently of this optical quenching. The negatively charged phosphate backbone increases (decreases) the DNA surface coverage on an areal basis at high (low) ionic strength, and is well described by a two-state equilibrium model. The resulting quantitative model is able to describe and link, for the first time, the observed changes in optical properties of DNA-wrapped SWCNTs with ionic strength, pH, adsorbed O2, and ascorbic acid. Cytosine nucleobases are shown to alter the adhesion of the DNA to SWCNTs through direct protonation from solution, decreasing the driving force for this phase transition. We show that the phase transition also changes the observed SWCNT corona phase, modulating the recognition of riboflavin. These results provide insight into the unique molecular interactions between DNA and the SWCNT surface, and have implications for molecular sensing, assembly, and nanoparticle separations.


Assuntos
DNA de Cadeia Simples/química , Nanotubos de Carbono/química , Concentração Osmolar , Transição de Fase , Adsorção , Ácido Ascórbico/química , Fluorescência , Concentração de Íons de Hidrogênio , Oxigênio/química , Riboflavina/química
15.
J Am Chem Soc ; 139(43): 15328-15336, 2017 11 01.
Artigo em Inglês | MEDLINE | ID: mdl-28985673

RESUMO

The concept of electrical energy generation based on asymmetric chemical doping of single-walled carbon nanotube (SWNT) papers is presented. We explore 27 small, organic, electron-acceptor molecules that are shown to tune the output open-circuit voltage (VOC) across three types of pristine SWNT papers with varying (n,m) chirality distributions. A considerable enhancement in the observed VOC, from 80 to 440 mV, is observed for SWNT/molecule acceptor pairs that have molecular volume below 120 Å3 and lowest unoccupied molecular orbital (LUMO) energies centered around -0.8 eV. The electron transfer (ET) rate constants driving the VOC generation are shown to vary with the chirality-associated Marcus theory, suggesting that the energy gaps between SWNT and the LUMO of acceptor molecules dictate the ET process. When the ET rate constants and the maximum VOC are plotted versus the LUMO energy of the acceptor organic molecule, volcano-shaped dependencies, characteristic of the Marcus inverted region, are apparent for three distinct sources of SWNT papers with modes in diameter distributions of 0.95, 0.83, and 0.75 nm. This observation, where the ET driving force exceeds reorganization energies, allows for an estimation of the outer-sphere reorganization energies with values as low as 100 meV for the (8,7) SWNT, consistent with a proposed image-charge modified Born energy model. These results expand the fundamental understanding of ET transfer processes in SWNT and allow for an accurate calculation of energy generation through asymmetric doping for device applications.

16.
J Nanobiotechnology ; 15(1): 19, 2017 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-28270155

RESUMO

Engineered nanomaterials (ENMs) are key drivers for the development of highly sophisticated new technologies. As all new attainments, the rapidly increasing used of ENMs raise concerns about their safety for the environment and humans. There is growing evidence showing that if engineered nanomaterials are released into the environment, there is a possibility that they could cause harm to aquatic microorganisms. Among the divers effects triggering their toxicity the ability of ENMs to generate reactive oxygen species (ROS) capable of oxidizing biomolecules is currently considered a central mechanism of toxicity. Therefore, development of sensitive tools for quantification of the ROS generation and oxidative stress are highly sought. After briefly introducing ENMs-induced ROS generation and oxidative stress in the aquatic microorganisms (AMOs), this overview paper focuses on a new optical biosensor allowing sensitive and dynamic measurements of H2O2 in real-time using multiscattering enhanced absorption spectroscopy. Its principle is based on sensitive absorption measurements of the heme protein cytochrome c whose absorption spectrum alters with the oxidation state of constituent ferrous FeII and ferric FeIII. For biological applications cytochrome c was embedded in porous random media resulting in an extended optical path length through multiple scattering of light, which lowers the limit of detection to a few nM of H2O2. The sensor was also integrated in a microfluidic system containing micro-valves and sieves enabling more complex experimental conditions. To demonstrate its performance, abiotic absorption measurements of low concentrations of dye molecules and 10 nm gold particles were carried out achieving limits of detection in the low nM range. Other biologically relevant reactive oxygen species can be measured at sub-µM concentrations, which was shown for glucose and lactate through enzymatic reactions producing H2O2. In ecotoxicological investigations H2O2 excreted by aquatic microorganisms exposed to various stressors were measured. Pro-oxidant effects of nano-TiO2 and nano-CuO towards green alga Chlamydomonas reinhardtii were explored in various exposure media and under different light illuminations. Dynamics of Cd2+ induced effects on photosynthetic activity, sensitisation and recovery of cells of C. reinhardtii was also studied.


Assuntos
Técnicas Biossensoriais/métodos , Chlamydomonas reinhardtii/efeitos dos fármacos , Cobre/toxicidade , Nanopartículas/toxicidade , Oxidantes/toxicidade , Titânio/toxicidade , Poluentes Químicos da Água/toxicidade , Técnicas Biossensoriais/instrumentação , Chlamydomonas reinhardtii/metabolismo , Desenho de Equipamento , Peróxido de Hidrogênio/análise , Peróxido de Hidrogênio/metabolismo , Dispositivos Lab-On-A-Chip , Estresse Oxidativo/efeitos dos fármacos
17.
Opt Express ; 24(22): A1306-A1320, 2016 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-27828518

RESUMO

Efficient optical energy transfer is key to many technologies, ranging from biosensing to photovoltaics. Here, for the first time we show that by introducing a random medium with appropriate filling factor, absorption in a specific volume can be maximized. Using both numerical simulations and an analytical diffusion model, we identify design rules to maximize absorption in the system with different geometrical and scattering properties. By combining a random medium with an open photonic cavity, we numerically demonstrate a 23-fold enhancement of the absorbed energy. We also show how absorption as high as 99% can be reached in a device as thin as 500 µm for normal incidence illumination. Finally, our data indicate that introducing a non-absorbing random medium into a light trapping system for thin solar cells can enhance absorption of energy by a factor of 2.2. This absorption enhancement, caused by the random medium, is broadband and wide-angle and can help design efficient solar cells, light trapping devices, biosensors and random lasers.

18.
Anal Chem ; 87(3): 1536-43, 2015 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-25546088

RESUMO

An original scheme for sensitive absorption measurements, particularly well-suited for low analyte concentrations, is presented. The technique is based on multiscattering-enhanced absorption spectroscopy (MEAS) and benefits from the advantages of conventional absorption spectroscopy: simplicity, rapidity, and low costs. The technique relies on extending the optical path through the sensing volume by suspending dielectric beads in the solution containing the analytes of interest, resulting in multiple scattering of light, which increases the optical path length through the sample. This way, a higher sensitivity and lower limit of detection, compared to those of conventional absorption spectroscopy, can be achieved. The approach is versatile and can be used for a broad variety of analytes. Here, it is applied to the detection of phenol red, 10 nm gold nanoparticles, and envy green fluorescence dye; the limit of detection is decreased by a factor of 7.2 for phenol red and a factor of 3.3 for nanoparticles and dye. The versatility of this approach is illustrated by its application in increasing the sensitivity of colorimetric detection with gold nanoparticle probes and a commercially available hydrogen peroxide bioassay. The influence of different parameters describing the scattering medium is investigated in detail experimentally and numerically, with very good agreement between the two. Those parameters can be effectively used to tailor the enhancement for specific applications and analytes.


Assuntos
Ouro/química , Nanopartículas Metálicas/química , Espectrofotometria/métodos , Corantes/análise , Luz , Método de Monte Carlo , Fenolsulfonaftaleína/análise , Espalhamento de Radiação
19.
ACS Nano ; 17(1): 240-250, 2023 01 10.
Artigo em Inglês | MEDLINE | ID: mdl-36524700

RESUMO

There is a pressing need for sensors and assays to monitor chemotherapeutic activity within the human body in real time to optimize drug dosimetry parameters such as timing, quantity, and frequency in an effort to maximize efficacy while minimizing deleterious cytotoxicity. Herein, we develop near-infrared fluorescent nanosensors based on single walled carbon nanotubes for the chemotherapeutic Temozolomide (TMZ) and its metabolite 5-aminoimidazole-4-carboxamide using Corona Phase Molecular Recognition as a synthetic molecular recognition technique. The resulting nanoparticle sensors are able to monitor drug activity in real-time even under in vivo conditions. Sensors can be engineered to be biocompatible by encapsulation in poly(ethylene glycol) diacrylate hydrogels. Selective detection of TMZ was demonstrated using U-87 MG human glioblastoma cells and SKH-1E mice with detection limits below 30 µM. As sensor implants, we show that such systems can provide spatiotemporal therapeutic information in vivo, as a valuable tool for pharmacokinetic evaluation. Sensor implants are also evaluated using intact porcine brain tissue implanted 2.1 cm below the cranium and monitored using a recently developed Wavelength-Induced Frequency Filtering technique. Additionally, we show that by taking the measurement of spatial and temporal analyte concentrations within each hydrogel implant, the direction of therapeutic flux can be resolved. In all, these types of sensors enable the real time detection of chemotherapeutic concentration, flux, directional transport, and metabolic activity, providing crucial information regarding therapeutic effectiveness.


Assuntos
Glioblastoma , Nanotubos de Carbono , Humanos , Animais , Camundongos , Suínos , Temozolomida , Glioblastoma/tratamento farmacológico , Corantes
20.
Nat Nanotechnol ; 17(6): 643-652, 2022 06.
Artigo em Inglês | MEDLINE | ID: mdl-35637357

RESUMO

Fluorescent nanosensors hold the potential to revolutionize life sciences and medicine. However, their adaptation and translation into the in vivo environment is fundamentally hampered by unfavourable tissue scattering and intrinsic autofluorescence. Here we develop wavelength-induced frequency filtering (WIFF) whereby the fluorescence excitation wavelength is modulated across the absorption peak of a nanosensor, allowing the emission signal to be separated from the autofluorescence background, increasing the desired signal relative to noise, and internally referencing it to protect against artefacts. Using highly scattering phantom tissues, an SKH1-E mouse model and other complex tissue types, we show that WIFF improves the nanosensor signal-to-noise ratio across the visible and near-infrared spectra up to 52-fold. This improvement enables the ability to track fluorescent carbon nanotube sensor responses to riboflavin, ascorbic acid, hydrogen peroxide and a chemotherapeutic drug metabolite for depths up to 5.5 ± 0.1 cm when excited at 730 nm and emitting between 1,100 and 1,300 nm, even allowing the monitoring of riboflavin diffusion in thick tissue. As an application, nanosensors aided by WIFF detect the chemotherapeutic activity of temozolomide transcranially at 2.4 ± 0.1 cm through the porcine brain without the use of fibre optic or cranial window insertion. The ability of nanosensors to monitor previously inaccessible in vivo environments will be important for life-sciences research, therapeutics and medical diagnostics.


Assuntos
Nanotubos de Carbono , Animais , Fluorescência , Corantes Fluorescentes , Peróxido de Hidrogênio , Camundongos , Riboflavina , Suínos
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