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1.
Photochem Photobiol ; 2021 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-34097752

RESUMO

This review describes nanoparticle and dye diffusion in bacterial biofilms in the context of antimicrobial photodynamic inactivation (aPDI). aPDI requires the diffusion of a photosensitizer (Sens) into the biofilm and subsequent photoactivation of oxygen for the generation of reactive oxygen species (ROS) that inactivate microbes. Molecular diffusion in biofilms has been long investigated, whereas this review is intended to draw a logical link between diffusion in biofilms and ROS, a combination that leads to the current state of aPDI and superhydrophobic aPDI (SH-aPDI). This review should be of interest to photochemists, photobiologists and researchers in material and antimicrobial sciences as is ties together conventional aPDI with the emerging subject of SH-aPDI.

2.
ACS Appl Mater Interfaces ; 10(30): 25819-25829, 2018 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-29972022

RESUMO

Singlet oxygen is a potent agent for the selective killing of a wide range of harmful cells; however, current delivery methods pose significant obstacles to its widespread use as a treatment agent. Limitations include the need for photosensitizer proximity to tissue because of the short (3.5 µs) lifetime of singlet oxygen in contact with water; the strong optical absorption of the photosensitizer, which limits the penetration depth; and hypoxic environments that restrict the concentration of available oxygen. In this article, we describe a novel superhydrophobic singlet oxygen delivery device for the selective inactivation of bacterial biofilms. The device addresses the current limitations by: immobilizing photosensitizer molecules onto inert silica particles; embedding the photosensitizer-containing particles into the plastron (i.e. the fluid-free space within a superhydrophobic surface between the solid substrate and fluid layer); distributing the particles along an optically transparent substrate such that they can be uniformly illuminated; enabling the penetration of oxygen via the contiguous vapor space defined by the plastron; and stabilizing the superhydrophobic state while avoiding the direct contact of the sensitizer to biomaterials. In this way, singlet oxygen generated on the sensitizer-containing particles can diffuse across the plastron and kill bacteria even deep within the hypoxic periodontal pockets. For the first time, we demonstrate complete biofilm inactivation (>5 log killing) of Porphyromonas gingivalis, a bacterium implicated in periodontal disease using the superhydrophobic singlet oxygen delivery device. The biofilms were cultured on hydroxyapatite disks and exposed to active and control surfaces to assess the killing efficiency as monitored by colony counting and confocal microscopy. Two sensitizer particle types, a silicon phthalocyanine sol-gel and a chlorin e6 derivative covalently bound to fluorinated silica, were evaluated; the biofilm killing efficiency was found to correlate with the amount of singlet oxygen detected in separate trapping studies. Finally, we discuss the applications of such devices in the treatment of periodontitis.


Assuntos
Biofilmes , Oxigênio , Fotoquimioterapia , Fármacos Fotossensibilizantes , Dióxido de Silício , Oxigênio Singlete
3.
ACS Appl Mater Interfaces ; 8(17): 10788-99, 2016 05 04.
Artigo em Inglês | MEDLINE | ID: mdl-27070413

RESUMO

Precise dispensing of nanoliter droplets is necessary for the development of sensitive and accurate assays, especially when the availability of the source solution is limited. Conventional approaches are limited by imprecise positioning, large shear forces, surface tension effects, and high costs. To address the need for precise and economical dispensing of nanoliter volumes, we developed a new approach where the dispensed volume is dependent on the size and shape of defined surface features, thus freeing the dispensing process from pumps and fine-gauge needles requiring accurate positioning. The surface we fabricated, called a nanoliter droplet virtual well microplate (nVWP), achieves high-precision dispensing (better than ±0.5 nL or ±1.6% at 32 nL) of 20-40 nL droplets using a small source drop (3-10 µL) on isolated hydrophilic glass pedestals (500 µm on a side) bonded to arrays of polydimethylsiloxane conical posts. The sharp 90° edge of the glass pedestal pins the solid-liquid-vapor triple contact line (TCL), averting the wetting of the glass sidewalls while the fluid is prevented from receding from the edge. This edge creates a sufficiently large energy barrier such that microliter water droplets can be poised on the glass pedestals, exhibiting contact angles greater >150°. This approach relieves the stringent mechanical alignment tolerances required for conventional dispensing techniques, shifting the control of dispensed volume to the area circumscribed by the glass edge. The effects of glass surface chemistry and dispense velocity on droplet volume were studied using optical microscopy and high-speed video. Functionalization of the glass pedestal surface enabled the selective adsorption of specific peptides and proteins from synthetic and natural biomolecule mixtures, such as venom. We further demonstrate how the nVWP dispensing platform can be used for a variety of assays, including sensitive detection of proteins and peptides by fluorescence microscopy or MALDI-TOF.


Assuntos
Nanoestruturas , Vidro , Interações Hidrofóbicas e Hidrofílicas , Proteínas , Molhabilidade
4.
Photochem Photobiol ; 92(1): 166-72, 2016.
Artigo em Inglês | MEDLINE | ID: mdl-26451683

RESUMO

We describe progress on a one-step photodynamic therapy (PDT) technique that is simple: device tip delivery of sensitizer, oxygen and light simultaneously. Control is essential for their delivery to target sites to generate singlet oxygen. One potential problem is the silica device tip may suffer from biomaterial fouling and the pace of sensitizer photorelease is slowed. Here, we have used biomaterial (e.g. proteins, cells, etc.) from SQ20B head and neck tumors and whole blood for an assessment of fouling of the silica tips by adsorption. It was shown that by exchanging the native silica tip for a fluorinated tip, a better nonstick property led to an increased sensitizer output by ~10%. The fluorinated tip gave a sigmoidal photorelease where singlet oxygen is stabilized to physical quenching, whereas the native silica tip with unprotected SiO-H groups gave a slower (pseudolinear) photorelease. A further benefit from fluorinated silica is that 15% less biomaterial adheres to its surface compared to native silica based on a bicinchoninic acid assay (BCA) and X-ray photoelectron spectroscopy (XPS) measurements. We discuss how the fluorination of the device tip increases biofouling resistance and can contribute to a new pointsource PDT tool.


Assuntos
Flúor/química , Neoplasias de Cabeça e Pescoço/tratamento farmacológico , Fotoquimioterapia/instrumentação , Materiais Biocompatíveis , Humanos
5.
ACS Appl Mater Interfaces ; 7(42): 23575-88, 2015 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-26372672

RESUMO

Condensation of water vapor is an essential process in power generation, water collection, and thermal management. Dropwise condensation, where condensed droplets are removed from the surface before coalescing into a film, has been shown to increase the heat transfer efficiency and water collection ability of many surfaces. Numerous efforts have been made to create surfaces which can promote dropwise condensation, including superhydrophobic surfaces on which water droplets are highly mobile. However, the challenge with using such surfaces in condensing environments is that hydrophobic coatings can degrade and/or water droplets on superhydrophobic surfaces transition from the mobile Cassie to the wetted Wenzel state over time and condensation shifts to a less-effective filmwise mechanism. To meet the need for a heat-transfer surface that can maintain stable dropwise condensation, we designed and fabricated a hybrid superhydrophobic-hydrophilic surface. An array of hydrophilic needles, thermally connected to a heat sink, was forced through a robust superhydrophobic polymer film. Condensation occurs preferentially on the needle surface due to differences in wettability and temperature. As the droplet grows, the liquid drop on the needle remains in the Cassie state and does not wet the underlying superhydrophobic surface. The water collection rate on this surface was studied using different surface tilt angles, needle array pitch values, and needle heights. Water condensation rates on the hybrid surface were shown to be 4 times greater than for a planar copper surface and twice as large for silanized silicon or superhydrophobic surfaces without hydrophilic features. A convection-conduction heat transfer model was developed; predicted water condensation rates were in good agreement with experimental observations. This type of hybrid superhydrophobic-hydrophilic surface with a larger array of needles is low-cost, robust, and scalable and so could be used for heat transfer and water collection applications.

6.
ACS Appl Mater Interfaces ; 7(4): 2632-40, 2015 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-25525836

RESUMO

Maintaining the long-term stability of superhydrophobic surfaces is challenging because of contamination from organic molecules and proteins that render the surface hydrophilic. Reactive oxygen species generated on a photocatalyst, such as TiO2, could mitigate this effect by oxidizing these contaminants. However, incorporation of such catalyst particles into a superhydrophobic surface is challenging because the particles become hydrophilic under UV exposure, causing the surface to transition to the Wenzel state. Here we show that a high concentration of hydrophilic TiO2 catalytic nanoparticles can be incorporated into a superhydrophobic surface by partially embedding the particles into a printed array of high aspect ratio polydimethylsiloxane posts. A stable Cassie state was maintained on these surfaces, even under UV irradiation, because of the significant degree of hierarchical roughness. By printing the surface on a porous support, oxygen could be flowed through the plastron, resulting in higher photooxidation rates relative to a static ambient. Rhodamine B and bovine serum albumin were photooxidized both in solution and after drying onto these TiO2-containing surfaces, and the effects of particle location and plastron gas composition were studied in static and flowing gas environments. This approach may prove useful for water purification, medical devices, and other applications where Cassie stability is required in the presence of organic compounds.

7.
Biomacromolecules ; 15(12): 4627-36, 2014 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-25346335

RESUMO

By bringing enzymes into contact with predefined regions of a surface, a polymer film can be selectively degraded to form desired patterns that find a variety of applications in biotechnology and electronics. This so-called "enzymatic lithography" is an environmentally friendly process as it does not require actinic radiation or synthetic chemicals to develop the patterns. A significant challenge to using enzymatic lithography has been the need to restrict the mobility of the enzyme in order to maintain control of feature sizes. Previous approaches have resulted in low throughput and were limited to polymer films only a few nanometers thick. In this paper, we demonstrate an enzymatic lithography system based on Candida antartica lipase B (CALB) and poly(ε-caprolactone) (PCL) that can resolve fine-scale features, (<1 µm across) in thick (0.1-2.0 µm) polymer films. A Polymer Pen Lithography (PPL) tool was developed to deposit an aqueous solution of CALB onto a spin-cast PCL film. Immobilization of the enzyme on the polymer surface was monitored using fluorescence microscopy by labeling CALB with FITC. The crystallite size in the PCL films was systematically varied; small crystallites resulted in significantly faster etch rates (20 nm/min) and the ability to resolve smaller features (as fine as 1 µm). The effect of printing conditions and relative humidity during incubation is also presented. Patterns formed in the PCL film were transferred to an underlying copper foil demonstrating a "Green" approach to the fabrication of printed circuit boards.


Assuntos
Proteínas Fúngicas/química , Lipase/química , Varredura Diferencial de Calorimetria , Caproatos/química , Lactonas/química , Microscopia de Força Atômica , Poliésteres/química , Polímeros/química , Propriedades de Superfície
8.
J Phys Chem A ; 118(45): 10364-71, 2014 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-24885074

RESUMO

We describe physical-organic studies of singlet oxygen generation and transport into an aqueous solution supported on superhydrophobic surfaces on which silicon-phthalocyanine (Pc) particles are immobilized. Singlet oxygen ((1)O2) was trapped by a water-soluble anthracene compound and monitored in situ using a UV-vis spectrometer. When oxygen flows through the porous superhydrophobic surface, singlet oxygen generated in the plastron (i.e., the gas layer beneath the liquid) is transported into the solution within gas bubbles, thereby increasing the liquid-gas surface area over which singlet oxygen can be trapped. Higher photooxidation rates were achieved in flowing oxygen, as compared to when the gas in the plastron was static. Superhydrophobic surfaces were also synthesized so that the Pc particles were located in contact with, or isolated from, the aqueous solution to evaluate the relative effectiveness of singlet oxygen generated in solution and the gas phase, respectively; singlet oxygen generated on particles wetted by the solution was trapped more efficiently than singlet oxygen generated in the plastron, even in the presence of flowing oxygen gas. A mechanism is proposed that explains how Pc particle wetting, plastron gas composition and flow rate as well as gas saturation of the aqueous solution affect singlet oxygen trapping efficiency. These stable superhydrophobic surfaces, which can physically isolate the photosensitizer particles from the solution may be of practical importance for delivering singlet oxygen for water purification and medical devices.


Assuntos
Gases/química , Oxigênio Singlete/química , Antracenos/química , Dimetilpolisiloxanos/química , Indóis/química , Microscopia Eletroquímica de Varredura , Nitrogênio/química , Nylons/química , Processos Fotoquímicos , Polimetil Metacrilato/química , Porosidade , Impressão/métodos , Compostos de Silício/química , Análise Espectral , Água/química , Molhabilidade
9.
J Am Chem Soc ; 135(50): 18990-8, 2013 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-24295210

RESUMO

We describe here a physical-organic study of the first triphasic superhydrophobic sensitizer for photooxidations in water droplets. Control of synthetic parameters enables the mechanistic study of "borderline" two- and three-phase superhydrophobic sensitizer surfaces where (1)O2 is generated in compartments that are wetted, partially wetted, or remain dry in the plastron (i.e., air layer beneath the droplet). The superhydrophobic surface is synthesized by partially embedding silicon phthalocyanine (Pc) sensitizing particles to specific locations on polydimethylsiloxane (PDMS) posts printed in a square array (1 mm tall posts on 0.5 mm pitch). In the presence of red light and oxygen, singlet oxygen is formed on the superhydrophobic surface and reacts with 9,10-anthracene dipropionate dianion (1) within a freestanding water droplet to produce an endoperoxide in 54-72% yields. Control of the (1)O2 chemistry was achieved by the synthesis of superhydrophobic surfaces enriched with Pc particles either at the PDMS end-tips or at PDMS post bases. Much of the (1)O2 that reacts with anthracene 1 in the droplets was generated by the sensitizer "wetted" at the Pc particle/water droplet interface and gave the highest endoperoxide yields. About 20% of the (1)O2 can be introduced into the droplet from the plastron. The results indicate that the superhydrophobic sensitizer surface offers a unique system to study (1)O2 transfer routes where a balance of gas and liquid contributions of (1)O2 is tunable within the same superhydrophobic surface.


Assuntos
Oxigênio/química , Fármacos Fotossensibilizantes/química , Interações Hidrofóbicas e Hidrofílicas , Microscopia Eletrônica de Varredura
10.
ACS Appl Mater Interfaces ; 5(18): 8915-24, 2013 Sep 25.
Artigo em Inglês | MEDLINE | ID: mdl-23889192

RESUMO

Multifunctional superhydrophobic nanocomposite surfaces based on photocatalytic materials, such as fluorosilane modified TiO2, have generated significant research interest. However, there are two challenges to forming such multifunctional surfaces with stable superhydrophobic properties: the photocatalytic oxidation of the hydrophobic functional groups, which leads to the permanent loss of superhydrophobicity, as well as the photoinduced reversible hydrolysis of the catalytic particle surface. Herein, we report a simple and inexpensive template lamination method to fabricate multifunctional TiO2-high-density polyethylene (HDPE) nanocomposite surfaces exhibiting superhydrophobicity, UV-induced reversible wettability, and self-cleaning properties. The laminated surface possesses a hierarchical roughness spanning the micro- to nanoscale range. This was achieved by using a wire mesh template to emboss the HDPE surface creating an array of polymeric posts while partially embedding untreated TiO2 nanoparticles selectively into the top surface of these features. The surface exhibits excellent superhydrophobic properties immediately after lamination without any chemical surface modification to the TiO2 nanoparticles. Exposure to UV light causes the surface to become hydrophilic. This change in wettability can be reversed by heating the surface to restore superhydrophobicity. The effect of TiO2 nanoparticle surface coverage and chemical composition on the mechanism and magnitude of wettability changes was studied by EDX and XPS. In addition, the ability of the surface to shed impacting water droplets as well as the ability of such droplets to clean away particulate contaminants was demonstrated.


Assuntos
Nanocompostos/química , Polietilenos/química , Titânio/química , Raios Ultravioleta , Catálise , Interações Hidrofóbicas e Hidrofílicas , Oxirredução , Propriedades de Superfície , Molhabilidade
11.
Environ Sci Technol ; 46(21): 12098-104, 2012 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-23075418

RESUMO

A microphotoreactor device was developed to generate bubbles (1.4 mm diameter, 90 µL) containing singlet oxygen at levels toxic to bacteria and fungus. As singlet oxygen decays rapidly to triplet oxygen, the bubbles leave behind no waste or byproducts other than O(2). From a comparative study in deaerated, air saturated, and oxygenated solutions, it was reasoned that the singlet oxygen bubbles inactivate Escherichia coli and Aspergillus fumigatus, mainly by an oxygen gradient inside and outside of the bubble such that singlet oxygen is solvated and diffuses through the aqueous solution until it reacts with the target organism. Thus, singlet oxygen bubble toxicity was inversely proportional to the amount of dissolved oxygen in solution. In a second mechanism, singlet oxygen interacts directly with E. coli that accumulate at the gas-liquid interface although this mechanism operates at a rate approximately 10 times slower. Due to encapsulation in the gaseous core of the bubble and a 0.98 ms lifetime, the bubbles can traverse relatively long 0.39 mm distances carrying (1)O(2) far into the solution; by comparison the diffusion distance of (1)O(2) fully solvated in H(2)O is much shorter (~150 nm). Bubbles that reached the outer air-water interface contained no (1)O(2). The mechanism by which (1)O(2) deactivated organisms was explored through the addition of detergent molecules and Ca(2+) ions. Results indicate that the preferential accumulation of E. coli at the air-water interface of the bubble leads to enhanced toxicity of bubbles containing (1)O(2). The singlet oxygen device offers intriguing possibilities for creating new types of disinfection strategies based on photodynamic ((1)O(2)) bubble carriers.


Assuntos
Aspergillus fumigatus/efeitos dos fármacos , Desinfetantes/farmacologia , Escherichia coli/efeitos dos fármacos , Oxigênio Singlete/farmacologia , Poluentes da Água , Aspergillus fumigatus/fisiologia , Desinfecção/métodos , Escherichia coli/fisiologia , Indóis , Lasers , Compostos de Organossilício , Fármacos Fotossensibilizantes
12.
Langmuir ; 28(5): 3053-60, 2012 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-22260325

RESUMO

Laser-coupled microphotoreactors were developed to bubble singlet oxygen [(1)O(2) ((1)Δ(g))] into an aqueous solution containing an oxidizable compound. The reactors consisted of custom-modified SMA fiberoptic receptacles loaded with 150 µm silicon phthalocyanine glass sensitizer particles, where the particles were isolated from direct contact with water by a membrane adhesively bonded to the bottom of each device. A tube fed O(2) gas to the reactor chambers. In the presence of O(2), singlet oxygen was generated by illuminating the sensitizer particles with 669 nm light from an optical fiber coupled to the top of the reactor. The generated (1)O(2) was transported through the membrane by the O(2) stream and formed bubbles in solution. In solution, singlet oxygen reacted with probe compounds (9,10-anthracene dipropionate dianion, trans-2-methyl-2-pentanoate anion, N-benzoyl-D,L-methionine, or N-acetyl-D,L-methionine) to give oxidized products in two stages. The early stage was rapid and showed that (1)O(2) transfer occurred via bubbles mainly in the bulk water solution. The later stage was slow; it arose only from (1)O(2)-probe molecule contact at the gas/liquid interface. A mechanism is proposed that involves (1)O(2) mass transfer and solvation, where smaller bubbles provide better penetration of (1)O(2) into the flowing stream due to higher surface-to-volume contact between the probe molecules and (1)O(2).


Assuntos
Oxigênio Singlete/química , Água/química , Gases/química , Indóis/síntese química , Indóis/química , Lasers , Estrutura Molecular , Compostos de Organossilício/síntese química , Compostos de Organossilício/química , Oxirredução , Fotoquímica/instrumentação , Fotoquímica/métodos , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química
13.
ACS Appl Mater Interfaces ; 3(9): 3508-14, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21797228

RESUMO

Fabricating robust superhydrophobic surfaces for commercial applications is challenging as the fine-scale surface features, necessary to achieve superhydrophobicity, are susceptible to mechanical damage. Herein, we report a simple and inexpensive lamination templating method to create superhydrophobic polymer surfaces with excellent abrasion resistance and water pressure stability. To fabricate the surfaces, polyethylene films were laminated against woven wire mesh templates. After cooling, the mesh was peeled from the polymer creating a 3D array of ordered polymer microposts on the polymer surface. The resulting texture is monolithic with the polymer film and requires no chemical modification to exhibit superhydrophobicity. By controlling lamination parameters and mesh dimensions, polyethylene surfaces were fabricated that exhibit static contact angles of 160° and slip angles of 5°. Chemical and mechanical stability was evaluated using an array of manual tests as well as a standard reciprocating abraser test. Surfaces remained superhydrophobic after more than 5500 abrasion cycles at a pressure of 32.0 kPa. In addition, the surface remains dry after immersing into water for 5 h at 55 kPa. This method is environmental friendly, as it employs no solvents or harsh chemicals and may provide an economically viable path to manufacture large areas of mechanically robust superhydrophobic surfaces from inexpensive polymers and reusable templates.


Assuntos
Polímeros/química , Interações Hidrofóbicas e Hidrofílicas , Polietileno/química , Pressão , Propriedades de Superfície , Água/química
14.
Langmuir ; 27(16): 9902-9, 2011 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-21699191

RESUMO

The fabrication and properties of superhydrophobic surfaces that exhibit ratchet-like anisotropic slip angle behavior is described. The surface is composed of arrays of poly(dimethylsiloxane) (PDMS) posts fabricated by a type of 3D printing. By controlling the dispense parameters, regular arrays of asymmetric posts were deposited such that the slope of the posts was varied from 0 to 50 relative to the surface normal. Advancing and receding contact angles as well as slip angles were measured as a function of the post slope and droplet volume. Ratchetlike slip angle anisotropy was observed on surfaces composed of sloped features. The maximum slip angle difference (for a 180° tilt angle variation) was 32° for 20 µL droplets on surfaces with posts fabricated with a slope of 50°. This slip angle anisotropy is attributed to an increase in the triple contact line (TCL) length as the droplet is tilted in a direction against the post slope whereas the TCL decreases continuously when the drop travels in a direction parallel to the post slope. The increasing length of the TCL creates an increased energy barrier that accounts for the higher slip angles in this direction.

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